Crystal forms of peptide molecules

Abstract

The present disclosure relates to crystalline forms of compounds useful in the synthesis of a peptides and processes for preparing the same.

Description

[0001] CRYSTAL FORMS OF PEPTIDE MOLECULES

[0002] Background

[0003] Development of synthetic peptide therapeutics has made great progress in the past decade, but efficient synthesis of peptides continues to represent a contemporary challenge, especially at large or industrial scale, where the accumulation of impurities and the ease and speed of product isolation are key concerns. Accordingly, provided herein are crystalline compounds and processes that are useful in the synthesis of synthetic peptide molecules.

[0004] Brief Summary

[0005] The present disclosure provides, inter alia, a crystalline form of a compound of Formula (XIV):

[0006] (XIV), or a pharmaceutically acceptable salt or solvate thereof.

[0007] In some embodiments, the crystalline form is an ethyl acetate (EtOAc) solvate. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as further comprising at least one peak selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as further comprising at least one peak selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having a XRPD pattern substantially as shown in FIG. 23.

[0008] In some embodiments, the crystalline form is a methyl tert-butyl ether (MTBE) solvate. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.4° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.2° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having a XRPD pattern substantially as shown in FIG. 22.

[0009] In some embodiments, the crystalline form is a 2-methyltetrahydrofuran (MeTHF) solvate. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.2° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having a XRPD pattern substantially as shown in FIG. 21.

[0010] In some embodiments, the crystalline form is an acetonitrile (MeCN) solvate. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.2° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having an XRPD pattern comprising peaks at 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having a XRPD pattern substantially as shown in FIG. 24.

[0011] The present disclosure further provides a process for preparing a crystalline EtOAc solvate form of the compound of Formula (XIV), wherein the process comprises: (1) forming a suspension of a compound of Formula (XIV) in a first solvent comprising acetonitrile, EtOAc, and water; and (2) adding a second solvent comprising EtOAc to provide the crystalline form.

[0012] The present disclosure further provides a process for preparing a crystalline MTBE solvate form of the compound of Formula (XIV), wherein the process comprises: (1) suspending a compound of Formula (XIV) in a first solvent comprising MeTHF; and (2) adding a second solvent consisting of MTBE to provide the crystalline form. The present disclosure further provides a process for preparing a crystalline MeTHF solvate form of the compound of Formula (XIV), wherein the process comprises: (1) suspending a compound of Formula (XIV) in a solvent comprising acetonitrile and water to form a crystallization mixture; and (2) performing constant volume distillation on the crystallization mixture by adding MeTHF at approximately the rate of distillation to form the crystalline form.

[0013] The present disclosure further provides a crystalline form of a compound of Formula (XV):

[0014] (XV), or a pharmaceutically acceptable salt or solvate thereof.

[0015] In some embodiments, the crystalline form has an average particle size of between about 20 pm and about 50 pm. In some embodiments, the crystalline form has an average particle size between about 25 pm and about 40 pm. In some embodiments, the crystalline form has an average particle size greater than about 20 pm. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.4° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.2° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having a XRPD pattern substantially as shown in FIG. 25.

[0016] The present disclosure further provides a process for preparing a crystalline form of the compound of Formula (XV), wherein the process comprises: (1) dissolving a compound of Formula (XV) in a first solvent comprising an alcohol and adding a second solvent comprising water to form a crystallization mixture; (2) adjusting the temperature of the crystallization mixture to a first temperature; (3) decreasing the temperature of the crystallization mixture to a second temperature, wherein the second temperature is lower than the first temperature; (4) repeating steps (2)-(3) at least once to provide the crystalline form.

[0017] The present disclosure further provides a crystalline form of a compound of Formula

[0018] (XIII):

[0019] (XIII), or a pharmaceutically acceptable salt or solvate thereof. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form is further characterized as having an XRPD pattern further comprising at least one peak selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form is characterized as having a XRPD pattern substantially as shown in FIG. 20.

[0020] Brief Description of the Drawings

[0021] FIG. 1 is an X-ray powder diffraction (XRPD) pattern of a crystalline form of the compound of Formula (II).

[0022] FIG. 2 is an XRPD pattern of a suspension of a crystalline form of the compound of Formula (III) in MeTHF.

[0023] FIG. 3 is an XRPD pattern of a suspension of a crystalline form of the compound of Formula (III) in MeTHF / MTBE (1 / 2).

[0024] FIG. 4 is an XRPD pattern of a crystalline form of the compound of Formula (IV).

[0025] FIG. 5 is an XRPD pattern of a crystalline form of the compound of Formula (V).

[0026] FIG. 6 is an XRPD pattern of a crystalline form of the compound of Formula (VI).

[0027] FIG. 7 is an XRPD pattern of a crystalline form of the compound of Formula (VI).

[0028] FIG. 8 is an XRPD pattern of a crystalline form of the compound of Formula (VI).

[0029] FIG. 9 is an XRPD pattern of a crystalline form of the compound of Formula (VI).

[0030] FIG. 10 is an XRPD pattern of a crystalline form of the compound of Formula (VII). FIG. 11 is an XRPD pattern of a crystalline form of the compound of Formula (VIII). FIG. 12 is an XRPD pattern of a crystalline form of the compound of Formula (IX).

[0031] FIG. 13 is an XRPD pattern of crystalline Form A of the compound of Formula (X).

[0032] FIG. 14 is an XRPD pattern of crystalline Form B of the compound of Formula (X).

[0033] FIG. 15 is an XRPD pattern of a crystalline form of the compound of Formula (XI).

[0034] FIG. 16 is an XRPD pattern of a crystalline form of the compound of Formula (XI).

[0035] FIG. 17 shows an XRPD pattern of a crystalline form of the compound of Formula (XI).

[0036] FIG. 18 is an XRPD pattern of a crystalline form of the compound of Formula (XI).

[0037] FIG. 19 is an XRPD pattern of a crystalline form of the compound of Formula (XII).

[0038] FIG. 20 is an XRPD pattern of a crystalline form of the compound of Formula (XIII).

[0039] FIG. 21 is an XRPD pattern of a crystalline form of a MeTHF solvate of a compound of Formula (XIV).

[0040] FIG. 22 is an XRPD pattern of a crystalline form of a MTBE solvate of a compound of Formula (XIV).

[0041] FIG. 23 is an XRPD pattern of a crystalline form of an EtOAc solvate of a compound of Formula (XIV).

[0042] FIG. 24 is an XRPD pattern of a crystalline form of a MeCN solvate of a compound of Formula (XIV).

[0043] FIG. 25 A is an XRPD pattern of one of the crystalline forms of the compound of Formula (XV).

[0044] FIG. 25B is an XRPD pattern of a crystalline form of the compound of Formula (XV).

[0045] FIG. 25C is an XRPD pattern of a crystalline form of the compound of Formula (XV).

[0046] FIG. 25D is an XRPD pattern of a crystalline form of the compound of Formula (XV).

[0047] FIG. 25E is an XRPD pattern of a crystalline form of the compound of Formula (XV).

[0048] FIG. 25F is an XRPD pattern of a crystalline form of the compound of Formula (XV).

[0049] FIG. 25G is an XRPD pattern of a crystalline form of the compound of Formula (XV).

[0050] FIG. 26 is a graph showing the particle size distribution of a crystalline form of the compound of Formula (XV).

[0051] FIG. 27 is a graph showing the filtration rate of a crystalline form of the compound of Formula (XV). The line 750 mbar (model) line represents the modeled value at 750 mbar. The experimental values overlay the modeled line. Detailed Description

[0052] Some embodiments relate to a compound of Formula (I):

[0053] (I). The compound of Formula (I) has an amino acid string of Ac-Pen*-N-T-W(7-Me)-Lys(Ac)- Pen*-Phe[4-(2-aminoethoxy)]-2Nal-THP-E-N-3Pal-Sarc-NH2, wherein Pen*- Pen* form a disulfide bond. The present disclosure relates to crystalline forms of intermediate compounds useful in the synthesis of the compound of Formula (I). As described in International Patent Application No. PCT / EP2023 / 082583, the disclosure of which is incorporated herein by reference in its entirety, compounds of Formulas (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), and (XV) as shown in Table A, are intermediates in the preparation of the compound of Formula (I). The present disclosure describes crystalline forms of these intermediate compounds and methods of making the same.

[0054] The crystalline intermediate compounds described herein are particularly advantageous because they can be produced on a large scale and can accordingly facilitate synthesis of the compound of Formula (I) on an industrial scale. Furthermore, preparation of the crystalline compounds of the present disclosure en route to the compound of Formula (I) can enhance the overall purity and yield and increase the speed of certain steps along the process, e.g., product isolation steps. Accordingly, an advantage of the processes for producing the crystalline compounds described herein is that they can be carried out on a large scale which is suitable for commercial manufacture. In some embodiments, the processes yield an amount of crystalline compound that is greater than 1 Kg, specifically an amount that is greater than 10 Kg, an amount that is greater than 20 Kg, an amount that is greater than 50 Kg, greater than 100 Kg, greater than 150 Kg, greater than 200 Kg. In some embodiments, the process yields an amount of crystalline compound in an amount that is between 10 Kg and 60 Kg.

[0055] Table A 1. Definitions

[0056] Unless otherwise defined herein, scientific and technical terms used in this disclosure shall have the meanings that are commonly understood by those of ordinary skill in the art.

[0057] As used in the specification and in the claims, the terms “comprise(s),” “comprising,” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named features, groups, ingredients, or steps and does not exclude the presence of additional features, groups, ingredients, or steps. The term “comprise(s),” “comprising,” “include(s),” “having,” “has,” “can,” or “contain(s),” can include embodiments encompassed by the term "consisting essentially of' or "consisting of."

[0058] “A,” “an,” or “a(n)”, is an indefinite article when used in reference to a group of substituents or “substituent group” herein, mean at least one.

[0059] “About” when referring to a value includes the stated value + / - 10% of the stated value. For example, about 50% includes a range of from 45% to 55%, while about 20 molar equivalents includes a range of from 18 to 22 molar equivalents. Accordingly, when referring to a range, “about” refers to each of the stated values + / - 10% of the stated value of each end of the range. For instance, a ratio of from about 1 to about 3 (weight / weight) includes a range of from 0.9 to 3.3. In some embodiments, reference to about a value or parameter includes a description of that value or parameter per se. For example, reference to about 20 molar equivalents includes and describes 20 molar equivalents per se.

[0060] The terms “peptide,” “polypeptide,” and “protein” are used interchangeably herein and typically refer to a molecule comprising a chain of two or more amino acids (e.g., L-amino acids, D-amino acids, modified amino acids, amino acid analogs, amino acid mimetics, etc.).

[0061] Naturally-occurring L-amino acids are represented by the conventional three-letter or capitalized one-letter amino acid designations of Table B. The corresponding D-amino acids are represented by lower-case one-letter amino acid designations or by the three-letter or capitalized one letter amino acid designations of Table 1 preceded by the letter “D” (e.g., r, dR, or D-Arg). Table B: Naturally-occurring amino acids

[0062] G Glycine Gly P Proline Pro

[0063] A Alanine Ala V Valine Vai L Leucine Leu I Isoleucine He M Methionine Met C Cysteine Cys F Phenylalanine Phe Y Tyrosine Tyr W Tryptophan Trp H Histidine His K Lysine Lys R Arginine Arg Q Glutamine Gin N Asparagine Asn E Glutamic Acid Glu D Aspartic Acid Asp

[0064] S Serine Ser T Threonine Thr

[0065] The term “L-amino acid,” as used herein, refers to the “L” isomeric form of an amino acid, and conversely the term “D-amino acid” refers to the “D” isomeric form of an amino acid (e.g., (D)Asp or D-Asp; (D)Phe or D-Phe). D-amino acids may be indicated as customary in lower case when referred to using single-letter abbreviations. For example, D-arginine can be represented as “arg” or “r.” Alternatively, a lower case “d” in front of an amino acid can be used to indicate that it is of the D isomeric form, for example D-lysine can be represented by dK.

[0066] In the case of less common or non-naturally occurring amino acids, unless they are referred to by their full name (e.g., sarcosine, ornithine, etc.), frequently employed three- or four- character codes are employed for residues thereof, including, Sar or Sarc (sarcosine, i.e., N- methylglycine), Aib (a-aminoisobutyric acid), Dab (2,4-diaminobutanoic acid), Dapa (2,3- diaminopropanoic acid), y-Glu (y-glutamic acid), Gaba (y-aminobutanoic acid), 0-Pro (pyrrolidine-3-carboxylic acid), and Abu (2-aminobutyric acid).

[0067] Unless indicated otherwise the names of naturally occurring and non-naturally occurring aminoacyl residues used herein follow the naming conventions suggested by the IUPAC Commission on the Nomenclature of Organic Chemistry and the IUPAC -TUB Commission on Biochemical Nomenclature as set out in “Nomenclature of a-Amino Acids (Recommendations, 1974)” Biochemistry, 14(2), (1975). To the extent that the names and abbreviations of amino acids and aminoacyl residues employed in this specification and appended claims differ from those suggestions, they will be made clear to the reader. In sequences of amino acids throughout the present disclosure, the individual amino acids are separated by a hyphen or brackets e.g, lysine is shown as [K],

[0068] The term “NH2,” as used herein, can refer to a free amino group present at the amino terminus of a polypeptide. The term “OH,” as used herein, can refer to a free carboxy group present at the carboxy terminus of a peptide. Further, the term “Ac,” as used herein, refers to Acetyl protection through acylation of the C- or N-terminus of a polypeptide. In certain peptides shown herein, the NH2 located at the C-terminus of the peptide indicates an amino group.

[0069] “Composition” as used herein is intended to encompass a product comprising the specified product ingredient, and which may include acceptable excipients, carriers or diluents (e.g., pharmaceutically acceptable excipients, carriers, or diluents) as described herein.

[0070] The term “pharmaceutically acceptable” indicates that the carrier(s), diluent(s) or excipient(s) must be compatible with the other components or ingredients of the compositions of the present disclosure, i.e., that which is useful, safe, non-toxic, and acceptable for pharmaceutical use. In accordance with the present disclosure pharmaceutically acceptable means approved or approvable as is listed in the U.S. Pharmacopoeia or other generally recognized pharmacopoeia for use in animals, and more particularly, in humans.

[0071] “Solvate” as used herein, means a physical association of a compound of the present disclosure with one or more solvent molecules. This physical association involves varying degrees of bonding, including hydrogen bonding. In certain instances, the solvate will be capable of isolation. The term “solvate” is intended to encompass both solution-phase and isolatable solvates. Non-limiting examples of suitable solvates include hydrates.

[0072] Provided are also pharmaceutically acceptable salts and tautomeric forms of the compounds described herein.

[0073] A “pharmaceutically acceptable salt” is intended to mean a salt of a free acid or base of peptides represented by Formula (I) that are non-toxic, biologically tolerable, or otherwise biologically suitable for administration to the subject. It should possess the desired pharmacological activity of the parent compound. See, generally, G.S. Paulekuhn, et al., “Trends in Active Pharmaceutical Ingredient Salt Selection based on Analysis of the Orange Book Database”, J. Med. Chem., 2007, 50:6665-72, S.M. Berge, et al., “Pharmaceutical Salts”, J Pharm Set., 1977, 66: 1-19, and Handbook of Pharmaceutical Salts, Properties, Selection, and Use, Stahl and Wermuth, Eds., Wiley-VCH and VHCA, Zurich, 2002. Examples of pharmaceutically acceptable salts are those that are pharmacologically effective and suitable for contact with the tissues of patients without undue toxicity, irritation, or allergic response. A peptide of Formula (I) may possess a sufficiently acidic group, a sufficiently basic group, or both types of functional groups, and accordingly react with a number of inorganic or organic bases, and inorganic and organic acids, to form a pharmaceutically acceptable salt.

[0074] “Tautomer” refers to alternate forms of a compound that differ in the position of a proton, such as enol-keto and imine-enamine tautomers, or the tautomeric forms of heteroaryl groups containing a ring atom attached to both a ring -NH- and a ring =N- such as pyrazoles, imidazoles, benzimidazoles, triazoles, and tetrazoles.

[0075] The term “alkyl” is a straight or branched saturated hydrocarbon. For example, an alkyl group can have 1 to 10 carbon atoms (i.e., (Ci-Cio)alkyl), 1 to 5 carbon atoms (i.e., (Ci-C5)alkyl), 1 to 4 carbon atoms (i.e., (Ci-C4)alkyl), or 1 to 3 carbon atoms (i.e., (Ci-C3)alkyl). Examples of alkyl groups include, but are not limited to, methyl (Me, -CFE), ethyl (Et, -CH2CH3), 1 -propyl ( / ?-Pr, w-propyl, -CH2CH2CH3), isopropyl (z-Pr, z-propyl, -CH(CH ,)2), 1 -butyl (zz-bu, zz-butyl, - CH2CH2CH2CH3), 2-butyl (.s-bu, .s-butyl, -CH(CH3)CH2CH3), / c / 7-butyl ( / -bu, / -butyl, - CH(CH3)3), 1 -pentyl (zz-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3) CH2CH2CH3), neopentyl (-CH2C(CH3)3), 1 -hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (- CH(CH3)CH2CH2CH2CH3), heptyl (-(CH2)6CH3), octyl (-(CH2)7CH3), 2,2,4-tnmethylpentyl (- CH2C(CH3)2CH2CH(CH3)2), nonyl (-(CH2)sCH3), decyl (-(CH2)9CH3), undecyl (-(CH2)IOCH3), and dodecyl (-(CH2)nCH3). In an embodiment, alkyl refers to C(i-6)alkyl. In another embodiment, alkyl refers to C(i-4)alkyl. In another embodiment, alkyl refers to C(i-3)alkyl.

[0076] The term “halo” or “halogen” refers to bromo (-Br), chloro (-C1), fluoro (-F), or iodo (-1). In an embodiment, halo refers to fluoro.

[0077] The term “haloalkyl” refers to a straight- or branched-chain alkyl group having from 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms in the chain optionally substituting one or more H with halo. Examples of “haloalkyl” groups include trifluoromethyl (CF3), difluoromethyl (CF2H), monofluoromethyl (CH2F), pentafluoroethyl (CF2CF3), tetrafluoroethyl (CHFCF3), monofluoroethyl (CH2CH2F), trifluoroethyl (CH2CF3), tetrafluor otrifluoromethylethyl (CF(CF3)2), and groups that in light of the ordinary skill in the art and the teachings provided herein would be considered equivalent to any one of the foregoing examples. In an embodiment, haloalkyl refers to C(i-6)haloalkyl. In another embodiment, haloalkyl refers to C(i-4)haloalkyl. In another embodiment, alkyl refers to C(i-3)haloalkyl.

[0078] An “alkoxy” group refers to an -O(alkyl) group, where alkyl is as defined herein. An “aryl” group refers to monocyclic, bicyclic (fused), and tricyclic (fused or spiro) hydrocarbon ring systems having a total of six to fourteen ring carbon atoms, wherein at least one ring in the system is aromatic and wherein each ring in the system contains 3 to 7 ring carbon atoms. For example, “aryl” can be “phenyl”.

[0079] The term “carboxy,” as used herein, refers to -CO2H.

[0080] Certain compounds of the present disclosure comprise protecting groups. The selection of appropriate protecting groups can be readily determined by one skilled in the art. The chemistry of protecting groups can be found, for example, in Greene, et al., Protective Groups in Organic Synthesis, 4d. Ed., Wiley & Sons, 2007.

[0081] Suitable amino protecting groups include benzyl (Bn), trityl (Trt), 4-methyltrityl (Mtt), 0- methoxyethoxytrityl (MEM), 2-nitrophenylsulfonyl (Nps), 2-(4- nitrophenyl)sulfonylethoxycarbonyl (Nsc), benzothiazole-2- sulfonyl (Bts), dithiasuccinoyl (Dts), nitrobenzenesulfonyl (Ns), 2-(2-nitrophenyl)propoxycarbonyl (NPPOC), 2-(3,4-methylenedioxy- 6-nitrophenyl)propoxycarbonyl (MNPPOC), methylsulfonylethoxycarbonyl (Msc) 9- fluorenylmethyloxycarbonyl (Fmoc), 2,7-di-terZ-butyl-Fmoc (Fmoc*), 2-fluoro-Fmoc (Fmoc(2F)), 2-monoisooctyl-Fmoc (mio-Fmoc), benzyloxycarbonyl (Cbz), 2,2,2- trichloroethoxycarbonyl (Troc), 2-(trimethylsilyl)ethoxycarbonyl (Teoc), 2-(4- trifluoromethylphenylsulfonyl)ethoxy carbonyl (Tsc), / c / 7-butoxy carbonyl (BOC), 1- adamantyloxycarbonyl (Adoc), 2-adamantyloxycarbonyl (2-Adoc), 2,4-dimethylpent-3- yloxy carbonyl (Doc), cyclohexyloxy carbonyl (Hoc), 1,1-dimethy 1-2, 2, 2-tri chloroethoxy carbonyl (TcBOC), formyl, acetyl (Ac), trifluoroacetyl (TFA), p-toluenesulfonyl (Ts), vinyl, 2-chloroethyl, 2-phenylsulfonylethyl, allyl, 2-nitrobenzyl, 4-nitrobenzyl, diphenyl-4-pyridylmethyl, N’,N’- dimethylhydrazinyl, methoxymethyl, / c / V-butoxymethyl (Bum), benzyloxymethyl (BOM), 2- tetrahydropyranyl (THP), tri(Ci-4 alkyl)silyl (e.g., tri(isopropyl)silyl), 1 , 1 -diethoxymethyl, a,a- dimethyl-3,5-dimethoxybenzyloxycarbonyl (Ddz), 2-(p-biphenylyl)-2-propyloxycarbonyl (Bpoc), 1,1 -di oxonaptho[l,2-b]thiophene-2-methyloxy carbonyl (a-Nsmoc), 3,3- dioxonaptho[2, 1 -b]thiophene-2-methyloxy carbonyl (0-Nsmoc), 1 -(4,4-dimethyl-2,6- dioxocyclohex-l-ylidene)ethyl (Dde), 1 -(4, 4-dimethyl-2,6-di oxocyclohex- 1 -ylidene)isovaleryl (ivDde), 2-(phenyl(methyl)sulfonio)ethoxycarbonyl (Pms), N-ethanesulfonylethoxycarbonyl (Esc), 2-(4-sulfophenylsulfonyl)ethoxycarbonyl (Sps), allyloxycarbonyl (Alloc), propargyloxycarbonyl (Poc), 9-(4-bromophenyl)-9-fluorenyl (BrPhF), azidomethyloxycarbonyl (Azoc), N-tetrachlorophthaloyl (TCP), phenyldithioethyloxycarbonyl (Phdec), 2- pyridyldithioethyloxycarbonyl (Pydec) or N-pivaloyloxymethyl (POM).

[0082] Suitable carboxyl protecting groups are selected from Ci-6 alkyl, such as tert-butyl (tBu), methyl (Me), ethyl (Et), propyl and cyclohexyl, allyl, 1 , 1 -dimethylallyl (Dma), phenacyl (Pac), p-nitrobenzyl (p-NB) trityl (Tr), 2-chlorotrityl (2-Cl-Trt), 2,4-dimethoxybenzyl (Dmb), 9- fluorenylmethyl (Fm), phenyl, cyclohexyl, benzyl (Bn), 3,4-ethylenedioxy-2-thenyl (EDOTn), 4- (N-(l-(4,4-diemthyl-2,6-dioxocyclohexylidene)-3-methylbutyl)amino)benzyl (Dmab), trimethylsilylethyl (TMSE), 2-(trimethylsilyl)isopropyl (Tmsi), 2,2,2-trichloroethyl (Tee), carbamoylmethyl (Cam), 4,5-dimethoxy-2-nitrobenzyloxycarbonyl (Dmnb), pentamine cobalt (III), P-menthyl (Men), P-3-menthylpent-3-yl (Mpe), or 2-phenylisopropyl (2-Ph(iPr)). In instances where the carboxyl protecting group also acts a leaving group in the amide coupling, the carboxyl protecting group can be p-nitrobenzyl.

[0083] Suitable thiol protecting groups include p-methyl benzyl (Meb), p-methoxybenzyl (Mob), trityl (Tr), monomethoxytrityl (Mmt), 2,4,6-trimethoxybenzyl (Tmob), 9-xanthenyl (Xan), 2,2,4,6,7-pentamethyl-5-dihydrobenzofuranylmethyl (Pmbf), benzyl (Bn), tert-butyl (tBu), 1- adamantyl (1-Ada), 9-fluorenylmethyl (Fm), 2-(2,4-dinitrophenyl)ethyl (Dnpe), 9- fluorenylmethyloxycarbonyl (Fmoc), acetamidomethyl (Acm), phenylacetamidomethyl (PhAcm), tert-butylmercapto (S(tBu)), 3-nitro-2-pyridinesulfenyl (Npys), 2-pyridinesulfenyl (S- Pyr), allyloxycarbonyl (Alloc), / V-allyloxycarbonyl- / V-[2,3,5,6-tetrafluoro-4- (phenylthio)phenyl)aminomethyl (Fsam), o-nitrobenzyl (o-NB), 4-Picolyl, ninhydrin (Nin).

[0084] Suitable hydroxyl protecting groups include benzyl (Bn), cyclohexyl, tert-butyl (tBu), trityl (Trt), tert-butyldimethylsilyl (TBDMS), pseudoprolines, tert-butyldiphenylsilyl (TBDPS), 4,5-dimethoxy-2-nitrobenzyloxycarbonyl (Dmnb), propargyloxycarbonyl (Poc).

[0085] The abbreviation, “(w / w)” refers to the phrase “weight for weight”, i.e., the proportion of a particular substance within a mixture, as measured by weight or mass or a weight amount of a component of the composition disclosed herein relative to the total weight amount of the composition. Accordingly, the quantity is unit less and represents a weight percentage amount of a component relative to the total weight of the composition. For example, a 2% (w / w) solution can indicate 2 grams of solute is dissolved in 100 grams of solution.

[0086] The abbreviation, “(V / V)” refers to the phrase “volume for volume”, i.e., the proportion of a particular substance within a mixture, as measured by volume or a volume amount of a component of the composition disclosed herein relative to the total volume amount of the composition. Accordingly, the quantity is unit less and represents a volume percentage amount of a component relative to the total volume of the composition. For example, a 2% (V / V) solvent mixture can indicate 2 mL of one solvent is present in 100 mb of the solvent mixture.

[0087] 2. Crystalline Form of a Compound of Formula (II)

[0088] The present disclosure provides a crystalline form of a compound of Formula (II):

[0089] (II), or a pharmaceutically acceptable salt or solvate thereof.

[0090] The compound of Formula (II) has an amino acid string of Fmoc-Pen(Acm)-Tyr(2-Boc- ea)-OMe.

[0091] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 6.1°, 9.6°, 12.8°, 15.3°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 6.1°, 9.6°, 12.8°, 15.3°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 6.1°, 9.6°, 12.8°, 15.3°, and 21.6° 20 ± 0.2° 20.

[0092] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising peaks at 6.1°, 9.6°, 12.8°, 15.3°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising peaks at 6.1°, 9.6°, 12.8°, 15.3°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising peaks at 6.1°, 9.6°, 12.8°, 15.3°, and 21.6° 20 ± 0.2° 20.

[0093] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least one peak selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least two peaks selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least three peaks selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least four peaks selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern further comprising at least five peaks selected from 12.1°, 19.8°, 20.3°, 20.4°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20.

[0094] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.2° 20.

[0095] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20.

[0096] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.2° 26.

[0097] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.2° 26. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising peaks at 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising peaks at 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern comprising peaks at 6.1°, 9.6°, 12.1°, 12.8°, 15.3°, 19.8°, 20.3°, 20.4°, 21.6°, 23.4°, 24.8°, and 26.4° 20 ± 0.2° 20.

[0098] In some embodiments, the crystalline form of the compound of Formula (II) is characterized as having an XRPD pattern substantially as shown in FIG. 1.

[0099] 3. Crystalline Form of a Compound of Formula (III)

[0100] The present disclosure further provides a composition comprising a crystalline form of a compound of Formula (III):

[0101] (III), or a pharmaceutically acceptable salt or solvate thereof.

[0102] The compound of Formula (III) has an amino acid string of Fmoc-Trp(7Me)-Lys(Ac)- Pen(Acm)-Tyr(2-Boc-ea)-OMe.

[0103] In some embodiments, the composition comprising the crystalline form of a compound of Formula (III) further comprises 2-methyltetrahydrofuran.

[0104] In some embodiments, the composition comprising the crystalline form of the compound of Formula (III) further comprises 2-methyltetrahydrofuran and methyl tert-butyl ether. In some embodiments, the 2-methyltetrahydrofuran and methyl tert-butyl ether are present in a ratio of about 1 :2 by volume.

[0105] In some embodiments, the composition comprising the crystalline form of the compound of Formula (III) has an XRPD pattern substantially as shown in FIG. 2. In some embodiments, the composition comprising the crystalline form of the compound of Formula (III) has an XRPD pattern substantially as shown in FIG. 3.

[0106] 4. Crystalline Form of a Compound of Formula (IV)

[0107] The present disclosure further provides a crystalline form of a compound of Formula

[0108] (IV), or a pharmaceutically acceptable salt or solvate thereof.

[0109] The compound of Formula (IV) has an amino acid string of Cbz-Asn-Thr(tBu)-OMe.

[0110] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.9°, 8.1°, 18.7°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.9°, 8.1°, 18.7°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.9°, 8.1°, 18.7°, and 21.6° 20 ± 0.2° 20.

[0111] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 18.7°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 18.7°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 18.7°, and 21.6° 20 ± 0.2° 20.

[0112] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern further comprising at least one, at least two, or at least three peaks selected from 10.5°, 11.2°, 14.3°, and 15.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern further comprising at least one, at least two, or at least three peaks selected from 10.5°, 11.2°, 14.3°, and 15.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern further comprising at least one peak selected from 10.5°, 11.2°, 14.3°, and 15.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 10.5°, 11.2°, 14.3°, and 15.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 10.5°, 11.2°, 14.3°, and 15.9° 20 ± 0.2° 20.

[0113] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, or at least seven peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, or at least seven peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, or at least seven peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.2° 20.

[0114] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.2° 20.

[0115] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.2° 20.

[0116] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, and 21.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, 21.6°, and 27.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, 21.6°, and 27.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern comprising peaks at 5.9°, 8.1°, 10.5°, 11.2°, 14.3°, 15.9°, 18.7°, 21.6°, and 27.4° 20 ± 0.2° 20.

[0117] In some embodiments, the crystalline form of the compound of Formula (IV) is characterized as having an XRPD pattern substantially as shown in FIG. 4.

[0118] 5. Crystalline Form of a Compound of Formula (V)

[0119] The present disclosure further provides a crystalline form of a compound of Formula (V):

[0120] (V), or a pharmaceutically acceptable salt or solvate thereof.

[0121] The compound of Formula (V) has an amino acid string of Fmoc-Pen(Trt)- Asn-Thr(tBu)- OMe.

[0122] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 6.6°, 12.4°, 14.2°, 18.9°, and 20.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 6.6°, 12.4°, 14.2°, 18.9°, and 20.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 6.6°, 12.4°, 14.2°, 18.9°, and 20.9° 20 ± 0.2° 20.

[0123] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 12.4°, 14.2°, 18.9°, and 20.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 12.4°, 14.2°, 18.9°, and 20.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 12.4°, 14.2°, 18.9°, and 20.9° 20 ± 0.2° 20.

[0124] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 9.9°, 11.3°, 13.4°, 15.6°, 16.3°, 17.0°, 18.2°, 19.7°, 20.6°, 22.8°, and 24.5° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern further comprising at least one peak selected from 9.9°, 11.3°, 13.4°, 15.6°, 16.3°, 17.0°, 18.2°, 19.7°, 20.6°, 22.8°, and 24.5° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern further comprising at least two peaks selected from 9.9°, 11.3°, 13.4°, 15.6°, 16.3°, 17.0°, 18.2°, 19.7°, 20.6°, 22.8°, and 24.5° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern further comprising at least three peaks selected from 9.9°, 11.3°, 13.4°, 15.6°, 16.3°, 17.0°, 18.2°, 19.7°, 20.6°, 22.8°, and 24.5° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern further comprising at least four peaks selected from 9.9°, 11.3°, 13.4°, 15.6°, 16.3°, 17.0°, 18.2°, 19.7°, 20.6°, 22.8°, and 24.5° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern further comprising at least five peaks selected from 9.9°, 11.3°, 13.4°, 15.6°, 16.3°, 17.0°, 18.2°, 19.7°, 20.6°, 22.8°, and 24.5° 20 ± 0.2° 20.

[0125] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.2° 20.

[0126] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 26 ± 0.2° 20.

[0127] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.2° 20.

[0128] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.2° 20.

[0129] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, and 24.5° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, 24.5°, and 26.8° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, 24.5°, and 26.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern comprising peaks at 6.6°, 9.9°, 11.3°, 12.4°, 13.4°, 14.2°, 15.6°, 16.3°, 17.0°, 18.2°, 18.9°, 19.7°, 20.6°, 20.9°, 22.8°, 24.5°, and 26.8° 20 ± 0.2° 20.

[0130] In some embodiments, the crystalline form of the compound of Formula (V) is characterized as having an XRPD pattern substantially as shown in FIG. 5.

[0131] 6. Crystalline Form of a Compound of Formula (VI)

[0132] The present disclosure further provides a crystalline form of a compound of Formula (VI): or a pharmaceutically acceptable salt or solvate thereof.

[0133] The compound of Formula (VI) has an amino acid string of Ac-Pen(Trt)-Asn-Thr(tBu)- OH.

[0134] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 7.7°, 10.0°, 14.0°, 17.8°, and 19.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 7.7°, 10.0°, 14.0°, 17.8°, and 19.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 7.7°, 10.0°, 14.0°, 17.8°, and 19.7° 26 ± 0.2° 20.

[0135] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising peaks at 7.7°, 10.0°, 14.0°, 17.8°, and 19.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising peaks at 7.7°, 10.0°, 14.0°, 17.8°, and 19.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising peaks at 7.7°, 10.0°, 14.0°, 17.8°, and 19.7° 20 ± 0.2° 20.

[0136] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 11.8°, 12.4°, 18.9°, 21.8°, and 24.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 11.8°, 12.4°, 18.9°, 21.8°, and 24.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern further comprising at least one peak selected from 11.8°, 12.4°, 18.9°, 21.8°, and 24.7° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern further comprising at least two peaks selected from 11.8°, 12.4°, 18.9°, 21.8°, and 24.7° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern further comprising at least three peaks selected from 11.8°, 12.4°, 18.9°, 21.8°, and 24.7° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern further comprising at least four peaks selected from 11.8°, 12.4°, 18.9°, 21.8°, and 24.7° 20 ± 0.2° 20.

[0137] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.2° 20.

[0138] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least four peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least four peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least four peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.2° 20.

[0139] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least six peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least six peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least six peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.2° 20.

[0140] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least eight peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least eight peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising at least eight peaks selected from 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising peaks at 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising peaks at 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern comprising peaks at 7.7°, 10.0°, 11.8°, 12.4°, 14.0°, 17.8°, 18.9°, 19.7°, 21.8°, and 24.7° 20 ± 0.2° 20.

[0141] In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern substantially as shown in FIG. 6. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern substantially as shown in FIG. 7. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern substantially as shown in FIG. 8. In some embodiments, the crystalline form of the compound of Formula (VI) is characterized as having an XRPD pattern substantially as shown in FIG. 9.

[0142] 7. Crystalline Form of a Compound of Formula (VII)

[0143] The present disclosure further provides a crystalline form of a compound of Formula (VII):

[0144] (V), or a pharmaceutically acceptable salt or solvate thereof.

[0145] The compound of Formula (VII) has an amino acid string of Boc-3Pal-Sarc-NH2.

[0146] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.8°, 9.5°, 19.0°, and 20.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.8°, 9.5°, 19.0°, and 20.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.8°, 9.5°, 19.0°, and 20.7° 20 ± 0.2° 20.

[0147] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising peaks at 5.8°, 9.5°, 19.0°, and 20.7° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising peaks at 5.8°, 9.5°, 19.0°, and 20.7° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising peaks at 5.8°, 9.5°, 19.0°, and 20.7° 20 ± 0.2° 20.

[0148] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least one peak selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least two peaks selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least three peaks selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least four peaks selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern further comprising at least five peaks selected from 17.3°, 17.7°, 18.4°, 19.9°, 23.7°, and 23.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.2° 20.

[0149] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.2° 20.

[0150] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.2° 20.

[0151] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.2° 20.

[0152] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising peaks at 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising peaks at 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern comprising peaks at 5.8°, 9.5°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.7°, 23.7°, and 23.9° 20 ± 0.2° 20.

[0153] In some embodiments, the crystalline form of the compound of Formula (VII) is characterized as having an XRPD pattern substantially as shown in FIG. 10.

[0154] 8. Crystalline Form of a Compound of Formula (VIII)

[0155] The present disclosure further provides a crystalline form of a compound of Formula (VIII):

[0156] (VIII), or a pharmaceutically acceptable salt or solvate thereof.

[0157] The compound of Formula (VIII) has an amino acid string of H-3Pal-Sarc-NH2.

[0158] In some embodiments, the crystalline form of the compound of Formula (VIII) is a hydrochloride salt. In some embodiments, the crystalline form of the compound of Formula (VIII) is a dihydrochloride salt.

[0159] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 16.0°, 21.4°, 21.9°, and 26.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 16.0°, 21.4°, 21.9°, and 26.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 16.0°, 21.4°, 21.9°, and 26.0° 20 ± 0.2° 20.

[0160] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 16.0°, 21.4°, 21.9°, and 26.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 16.0°, 21.4°, 21.9°, and 26.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 16.0°, 21.4°, 21.9°, and 26.0° 20 ± 0.2° 20.

[0161] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern further comprising at least one, at least two, or at least three peaks selected from 9.1°, 18.8°, 22.3°, and 25.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern further comprising at least one, at least two, or at least three peaks selected from 9.1°, 18.8°, 22.3°, and 25.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern further comprising at least one peak selected from 9.1°, 18.8°, 22.3°, and 25.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern further comprising at least two peaks selected from 9.1°, 18.8°, 22.3°, and 25.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern further comprising at least three peaks selected from 9.1°, 18.8°, 22.3°, and 25.6° 20 ± 0.2° 20.

[0162] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, or at least seven peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VUI) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, or at least seven peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, or at least seven peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.2° 20.

[0163] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least four peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least four peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least four peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.2° 20.

[0164] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least six peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least six peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising at least six peaks selected from 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.2° 20.

[0165] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, and 26.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, 26.0°, 27.6°, and 28.8° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, 26.0°, 27.6°, and 28.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern comprising peaks at 9.1°, 16.0°, 18.8°, 21.4°, 21.9°, 22.3°, 25.6°, 26.0°, 27.6°, and 28.8° 20 ± 0.2° 20.

[0166] In some embodiments, the crystalline form of the compound of Formula (VIII) is characterized as having an XRPD pattern substantially as shown in FIG. 11.

[0167] 9. Crystalline Form of a Compound of Formula (IX)

[0168] The present disclosure further provides a crystalline form of a compound of Formula (IX):

[0169] (IX), or a pharmaceutically acceptable salt or solvate thereof.

[0170] The compound of Formula (IX) has an amino acid string of Cbz-Glu(tBu)-Asn-H.

[0171] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.6°, 15.4°, 17.8°, 18.5°, 18.9°, and 24.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.6°, 15.4°, 17.8°, 18.5°, 18.9°, and 24.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.6°, 15.4°, 17.8°, 18.5°, 18.9°, and 24.0° 20 ± 0.2° 20.

[0172] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising peaks at 4.6°, 15.4°, 17.8°, 18.5°, 18.9°, and 24.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising peaks at 4.6°, 15.4°, 17.8°, 18.5°, 18.9°, and 24.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising peaks at 4.6°, 15.4°, 17.8°, 18.5°, 18.9°, and 24.0° 20 ± 0.2° 20.

[0173] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least one peak selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least two peaks selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least three peaks selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least four peaks selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern further comprising at least five peaks selected from 8.0°, 10.2°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.3°, 25.3° 20 ± 0.2° 20.

[0174] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.2° 20.

[0175] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.2° 20.

[0176] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.2° 20.

[0177] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least ten peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least ten peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising at least ten peaks selected from 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.2° 20.

[0178] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising peaks at 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising peaks at 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern comprising peaks at 4.6°, 8.0°, 10.2°, 15.4°, 17.8°, 18.5°, 18.9°, 19.9°, 20.4°, 21.8°, 23.0°, 23.3°, 23.6°, 24.0°, 24.3°, 25.3° 20 ± 0.2° 20.

[0179] In some embodiments, the crystalline form of the compound of Formula (IX) is characterized as having an XRPD pattern substantially as shown in FIG. 12.

[0180] 10. Crystalline Forms of a Compound of Formula (X)

[0181] The present disclosure further provides a crystalline form of a compound of Formula (X):

[0182] (X), or a pharmaceutically acceptable salt or solvate thereof.

[0183] The compound of Formula (X) has an amino acid string of Cbz-Glu(tBu)-Asn-3Pal-Sarc-

[0184] NH2.

[0185] 10.1. Crystalline Form A of a Compound of Formula (X) In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.3°, 5.3°, 8.6°, 16.2°, and 20.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.3°, 5.3°, 8.6°, 16.2°, and 20.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.3°, 5.3°, 8.6°, 16.2°, and 20.0° 20 ± 0.2° 20.

[0186] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.3°, 5.3°, 8.6°, 16.2°, and 20.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.3°, 5.3°, 8.6°, 16.2°, and 20.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.3°, 5.3°, 8.6°, 16.2°, and 20.0° 20 ± 0.2° 20.

[0187] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 8.1°, 11.8°, 14.5°, 21.8°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 8.1°, 11.8°, 14.5°, 21.8°, and 22.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least one peak selected from 8.1°, 11.8°, 14.5°, 21.8°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least two peaks selected from 8.1°, 11.8°, 14.5°, 21.8°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least three peaks selected from 8.1°, 11.8°, 14.5°, 21.8°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least four peaks selected from 8.1°, 11.8°, 14.5°, 21.8°, and 22.4° 20 ± 0.2' 20.

[0188] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.2° 20.

[0189] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.2° 20.

[0190] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.2° 20.

[0191] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.2° 20.

[0192] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.3°, 5.3°, 8.1°, 8.6°, 11.8°, 14.5°, 16.2°, 20.0°, 21.8°, and 22.4° 20 ± 0.2° 20.

[0193] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern substantially as shown in FIG. 13.

[0194] 10.2. Crystalline Form B of a Compound of Formula (X)

[0195] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, and 15.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, and 15.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, and 15.4° 20 ± 0.2° 20.

[0196] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.6°, 5.2°, 7.6°, 9.2°, and 15.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.6°, 5.2°, 7.6°, 9.2°, and 15.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.6°, 5.2°, 7.6°, 9.2°, and 15.4° 20 ± 0.2° 20.

[0197] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 11.2°, 13.8°, 21.1°, 21.7°, and 23.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 11.2°, 13.8°, 21.1°, 21.7°, and 23.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least one peak selected from 11.2°, 13.8°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least two peaks selected from 11.2°, 13.8°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least three peaks selected from 11.2°, 13.8°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern further comprising at least four peaks selected from 11.2°, 13.8°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20.

[0198] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20.

[0199] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20.

[0200] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20.

[0201] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20.

[0202] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern comprising peaks at 4.6°, 5.2°, 7.6°, 9.2°, 11.2°, 13.8°, 15.4°, 21.1°, 21.7°, and 23.6° 20 ± 0.2° 20.

[0203] In some embodiments, the crystalline form of the compound of Formula (X) is characterized as having an XRPD pattern substantially as shown in FIG. 14. 11. Crystalline Form of a Compound of Formula (XI)

[0204] The present disclosure further provides a crystalline form of a compound of Formula (XI):

[0205] (XI), or a pharmaceutically acceptable salt or solvate thereof.

[0206] The compound of Formula (XI) has an amino acid string of Fmoc-2Nal-THP-OH.

[0207] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.4°, 10.8°, 11.5°, and 16.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.4°, 10.8°, 11.5°, and 16.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 5.4°, 10.8°, 11.5°, and 16.5° 20 ± 0.2° 20.

[0208] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising peaks at 5.4°, 10.8°, 11.5°, and 16.5° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising peaks at 5.4°, 10.8°, 11.5°, and 16.5° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising peaks at 5.4°, 10.8°, 11.5°, and 16.5° 20 ± 0.2° 20.

[0209] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern further comprising at least one or at least two peaks selected from 15.9°, 20.9°, and 22.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern further comprising at least one or at least two peaks selected from 15.9°, 20.9°, and 22.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern further comprising at least one peak selected from 15.9°, 20.9°, and 22.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern further comprising at least two peaks selected from 15.9°, 20.9°, and 22.9° 20 ± 0.2° 20.

[0210] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least three, at least four, at least five, or at least six peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least three, at least four, at least five, or at least six peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least three, at least four, at least five, or at least six peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.2° 20.

[0211] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least three peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least three peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least three peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.2° 20.

[0212] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising at least four peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD patern comprising at least four peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 26 ± 0.2° 20.

[0213] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD patern comprising at least five peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD patern comprising at least five peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.3° 20.In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD patern comprising at least five peaks selected from 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.2° 20.

[0214] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD patern comprising peaks at 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising peaks at 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern comprising peaks at 5.4°, 10.8°, 11.5°, 15.9°, 16.5°, 20.9°, and 22.9° 20 ± 0.2° 20.

[0215] In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern substantially as shown in FIG. 15. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern substantially as shown in FIG. 16. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD patern substantially as shown in FIG. 17. In some embodiments, the crystalline form of the compound of Formula (XI) is characterized as having an XRPD pattern substantially as shown in FIG. 18.

[0216] 12. Crystalline Form of a Compound of Formula (XII)

[0217] The present disclosure further provides a crystalline form of a compound of Formula

[0218] (XII):

[0219] (XII), or a pharmaceutically acceptable salt or solvate thereof.

[0220] The compound of Formula (XII) has an amino acid string of Fmoc-2Nal-THP-Glu(tBu)- Asn-3Pal-Sarc-NH2.

[0221] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 4.3°, 7.5°, 15.1°, and 18.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 4.3°, 7.5°, 15.1°, and 18.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 4.3°, 7.5°, 15.1°, and 18.3° 20 ± 0.2° 20.

[0222] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising peaks at 4.3°, 7.5°, 15.1°, and 18.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising peaks at 4.3°, 7.5°, 15.1°, and 18.3° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising peaks at 4.3°, 7.5°, 15.1°, and 18.3° 20 ± 0.2° 20.

[0223] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 11.4°, 16.8°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, or at least four peaks selected from 11.4°, 16.8°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern further comprising at least one peak selected from 11.4°, 16.8°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern further comprising at least two peaks selected from 11.4°, 16.8°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern further comprising at least three peaks selected from 11.4°, 16.8°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern further comprising at least four peaks selected from 11.4°, 16.8°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20.

[0224] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20.

[0225] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20.

[0226] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20.

[0227] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising peaks at 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising peaks at 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern comprising peaks at 4.3°, 7.5°, 11.4°, 15.1°, 16.8°, 18.3°, 19.2°, 21.0°, 22.0°, 22.5°, and 25.2° 20 ± 0.2° 20.

[0228] In some embodiments, the crystalline form of the compound of Formula (XII) is characterized as having an XRPD pattern substantially as shown in FIG. 19. 13. Crystalline Form of a Compound of Formula (XIII)

[0229] The present disclosure further provides a crystalline form of a compound of Formula (XIII):

[0230] (XIII), or a pharmaceutically acceptable salt or solvate thereof.

[0231] The compound of Formula (XIII) has an amino acid string of Ac-Pen(Trt)-Asn-Thr(tBu)- Trp(7Me)-Lys(Ac)-Pen(Acm)-Tyr(2-Boc-ea)-OH.

[0232] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.2° 20.

[0233] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising peaks at 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising peaks at 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising peaks at 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.2° 20.

[0234] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern further comprising at least one peak selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern further comprising at least two peaks selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern further comprising at least three peaks selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern further comprising at least four peaks selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern further comprising at least five peaks selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.2° 20.

[0235] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.2° 20.

[0236] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least six peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least six peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least six peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.2° 20.

[0237] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least eight peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.2° 20.

[0238] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least ten peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least ten peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising at least ten peaks selected from 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.2° 20.

[0239] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising peaks at 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising peaks at 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern comprising peaks at 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 26 ± 0.2° 20.

[0240] In some embodiments, the crystalline form of the compound of Formula (XIII) is characterized as having an XRPD pattern substantially as shown in FIG. 20.

[0241] 14. Crystalline Forms of a Compound of Formula (XIV)

[0242] The present disclosure further provides a crystalline form of a compound of Formula

[0243] (XIV):

[0244] (XIV), or a pharmaceutically acceptable salt or solvate thereof.

[0245] The compound of Formula (XIV) has an amino acid string of Ac-Pen* -Asn-Thr(tBu)- Trp(7Me)-Lys(Ac)-Pen*-Tyr(2-Boc-ea)-OH, wherein Pen* and Pen* form a disulfide bond.

[0246] In some embodiments, the crystalline form of the compound of Formula (XIV) has a purity of at least 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90% by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) has a purity of at least 75% by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) has a purity of at least 80% by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) has a purity of at least 85% by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) has a purity of at least 90% by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) has a purity of at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 25% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 20% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 15% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 10% non-solvent impurities by weight.

[0247] In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 8% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 6% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 4% non-solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 2% non-solvent impurities by weight.

[0248] In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 15% solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 10% solvent impurities by weight. In some embodiments, the crystalline form of the compound of Formula (XIV) comprises fewer than 10%, 9%, 8%, 7%, 6%, 4%, 3%, 2%, or 1% solvent impurities by weight. As used herein, the term “solvent impurities” encompasses both organic solvents and water.

[0249] In some embodiments, the crystalline form of the compound of Formula (XIV) is a solvate.

[0250] 14.1. Crystalline 2 -Methyltetrahydrofuran Solvate Form of a Compound of Formula (XI f

[0251] In some embodiments, the crystalline form of the compound of Formula (XIV) is a 2- methyltetrahydrofuran (MeTHF) solvate.

[0252] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.2° 20.

[0253] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.2° 20.

[0254] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one peak selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20.

[0255] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20.

[0256] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20.

[0257] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20.

[0258] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 26 ± 0.2° 26.

[0259] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern substantially as shown in FIG. 21.

[0260] 14.2. Crystalline Methyl Tert-Butyl Ether Solvate Form of a Compound of Formula (XIV)

[0261] In some embodiments, the crystalline form of the compound of Formula (XIV) is a methyl tert-butyl ether (MTBE) solvate.

[0262] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 4.8°, 14.3°, 19.9°, and 20.8° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 4.8°, 14.3°, 19.9°, and 20.8° 26 ± 0.2° 26.

[0263] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.8°, 14.3°, 19.9°, and 20.8° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.2° 20.

[0264] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one peak selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 20 ± 0.2° 20.

[0265] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.2° 20.

[0266] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.2° 20.

[0267] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.2° 20.

[0268] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 26 ± 0.2° 20.

[0269] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern substantially as shown in FIG. 22.

[0270] 14.3. Crystalline Ethyl Acetate Solvate Form of a Compound of Formula (XI V)

[0271] In some embodiments, the crystalline form of the compound of Formula (XIV) is an ethyl acetate (EtOAc) solvate.

[0272] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least two, at least three, at least four, or at least five peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least two, at least three, at least four, or at least five peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least two, at least three, at least four, or at least five peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.2° 26.

[0273] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.2° 26.

[0274] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one peak selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.2° 26.

[0275] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.2° 26.

[0276] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20.

[0277] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20.

[0278] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20.

[0279] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.2° 20.

[0280] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern substantially as shown in FIG. 23.

[0281] The crystalline EtOAc solvate form of the compound of Formula (XIV) is of particular utility in the synthesis of the compound of Formula (I) because it can be prepared with particularly high purity. Specifically, the crystalline EtOAc solvate form of the compound of Formula (XIV) can be prepared with a purity of at least 90% by weight or with fewer than 2% non-solvent impurities by weight.

[0282] Accordingly, in some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) has a purity of at least 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90% by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) has a purity of at least 75% by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) has a purity of at least 80% by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) has a purity of at least 85% by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) has a purity of at least 90% by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) has a purity of at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% by weight.

[0283] In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 25% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 20% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 15% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 10% non-solvent impurities by weight.

[0284] In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 8% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 6% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 4% non-solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 2% non-solvent impurities by weight.

[0285] In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 15% solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 10% solvent impurities by weight. In some embodiments, the crystalline EtOAc solvate form of the compound of Formula (XIV) comprises fewer than 10%, 9%, 8%, 7%, 6%, 4%, 3%, 2%, or 1% solvent impurities by weight.

[0286] 14.4. Crystalline Acetonitrile Solvate Form of a Compound of Formula (XI V)

[0287] In some embodiments, the crystalline form of the compound of Formula (XIV) is an acetonitrile (MeCN) solvate.

[0288] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least one, at least two, or at least three peaks selected from 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.2° 20.

[0289] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least one peak selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20.

[0290] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four, at least five, at least six, at least seven, or at least eight peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least four peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20.

[0291] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least six peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20.

[0292] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20.

[0293] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern comprising peaks at 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.2° 20.

[0294] In some embodiments, the crystalline form of the compound of Formula (XIV) is characterized as having an XRPD pattern substantially as shown in FIG. 24.

[0295] 14.5. Processes for Preparing a Crystalline Form of the Compound of Formula (XI V) The present disclosure further provides processes for preparing a crystalline form of a compound of Formula (XIV’).

[0296] R1-X3a-X4a-X5a-X6a-X7a-X8a-X9a-X10a-R3

[0297] (XIV’), or a pharmaceutically acceptable salt or solvate thereof, wherein

[0298] R1is H or Ci-20 alkanoyl;

[0299] R3is OH or OP2;

[0300] P2is a carboxyl protecting group;

[0301] X3a is absent or any amino acid residue;

[0302] X4a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0303] X5a is Cit, Glu, Gly, substituted Gly, Leu, He, beta- Ala, Ala, Lys, Asn, Pro, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), Gin, Asp, or Cys;

[0304] X6a is Thr, Aib, Asp, Dab, Gly, Pro, Ser, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha- MeAsn, alpha-MeThr, alpha-MeSer, or Vai;

[0305] X7a is unsubstituted Trp, or Trp substituted with cyano, halo, alkyl, substituted or unsubstituted aryl, haloalkyl, hydroxy, or alkoxy;

[0306] X8a is Gin, alpha-MeLys, alpha-MeLeu, alpha-MeLys(Ac), beta-homoGln, Cit, Glu, Phe, Asn, Thr, Vai, Aib, alpha-MeGln, alpha-MeAsn, Lys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), INal, 2Nal, or Trp;

[0307] X9a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0308] XI 0a is unsubstituted Phe, or Phe substituted with halo, alkyl, haloalkyl, hydroxy, alkoxy, carboxy, carboxamido, 2-aminoethoxy, or 2-acetylaminoethoxy; and the compound is cyclized via a disulfide or thioether bond between X4a and X9a; wherein the side chains of each of the amino acid residues are independently optionally protected by suitable protecting groups.

[0309] In some embodiments of the processes for preparing a crystalline form of the compound of Formula (XIV’):

[0310] R1is H or Ci-20 alkanoyl;

[0311] R3is OH or OP2;

[0312] P2is a carboxyl protecting group;

[0313] X3a is absent or any amino acid residue;

[0314] X4a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0315] X5a is Cit, Glu, Gly, substituted Gly, Leu, He, beta- Ala, Ala, Lys, Asn, Pro, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), Gin, Asp, or Cys;

[0316] X6a is Thr, protected Thr, Aib, Asp, Dab, Gly, Pro, Ser, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha- MeAsn, alpha-MeThr, alpha-MeSer, or Vai;

[0317] X7a is unsubstituted Trp, or Trp substituted with cyano, halo, alkyl, substituted or unsubstituted aryl, haloalkyl, hydroxy, or alkoxy;

[0318] X8a is Gin, alpha-MeLys, alpha-MeLeu, alpha-MeLys(Ac), beta-homoGln, Cit, Glu, Phe, Asn, Thr, Vai, Aib, alpha-MeGln, alpha-MeAsn, Lys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), INal, 2Nal, or Trp;

[0319] X9a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0320] XI 0a is unsubstituted Phe, or Phe substituted with halo, alkyl, haloalkyl, hydroxy, protected hydroxy, alkoxy, carboxy, protected carboxy, carboxamido, protected carboxamido, 2- aminoethoxy, protected 2-aminoethoxy, or 2-acetylaminoethoxy; and the compound is cyclized via a disulfide or thioether bond between X4a and X9a.

[0321] In some embodiments, X3a is absent

[0322] In some embodiments, X4a is Abu or Pen. In some embodiments, X4a is Pen.

[0323] In some embodiments, X5a is Cit, Glu, Gly, Leu, He, Ala, Lys, Asn, alpha-MeGln, alpha- MeLys, alpha-MeLeu, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo- Lys(Ac), Gin, or Asp. In some embodiments, X5a is Cit, Glu, Asn, alpha-MeGln, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), Gin, or Asp. In some embodiments, X5a is Asn.

[0324] In some embodiments, X6a is protected Thr. In some embodiments, X6a is Thr(tBu).

[0325] In some embodiments, X7a is Trp substituted with alkyl or substituted or unsubstituted aryl. In some embodiments, X7a is Trp(7Me).

[0326] In some embodiments, X8a is Gin, alpha-Me-Lys, alpha-MeLys(Ac), Asn, Aib, alpha- MeGln, alpha-MeAsn, Lys(Ac), Dab(Ac), Dap(Ac), or homo-Lys(Ac). In some embodiments, X8a is Gin, Lys(Ac), Dab(Ac), Dap(Ac), or homo-Lys(Ac). In some embodiments, X8a is Lys(Ac)).

[0327] In some embodiments, X9a is Cys, alpha-MeCys, or Pen. In some embodiments, X9a is

[0328] Pen.

[0329] In some embodiments, XI Oa is Phe substituted with protected 2-aminoethoxy. In some embodiments, XI Oa is Tyr(2-Boc-ea).

[0330] In some embodiments, the compound of Formula (XIV’) is a compound of Formula (XIV):

[0331] (XIV).

[0332] Accordingly, the present disclosure further provides processes for preparing a crystalline form of the compound of Formula (XIV).

[0333] In one aspect, the disclosure provides a process for preparing a crystalline MeTHF solvate form of the compound of Formula (XIV’), wherein the process comprises: (1) suspending a compound of Formula (XIV’) in a solvent comprising acetonitrile and water to form a crystallization mixture; and

[0334] (2) performing constant volume distillation on the crystallization mixture by adding MeTHF at approximately the rate of distillation to form the crystalline form.

[0335] In an embodiment, the disclosure provides a process for preparing a crystalline MeTHF solvate form of the compound of Formula (XIV), wherein the process comprises:

[0336] (1) suspending a compound of Formula (XIV) in a solvent comprising acetonitrile and water to form a crystallization mixture; and

[0337] (2) performing constant volume distillation on the crystallization mixture by adding MeTHF at approximately the rate of distillation to form the crystalline form.

[0338] In some embodiments, the solvent further comprises sodium bisulfate.

[0339] In some embodiments, the solvent has a pH between about 5 and about 2. In some embodiments, the solvent has a pH between about 2.5 and about 3.5. In some embodiments, the solvent has a pH of about 3.0.

[0340] In some embodiments, the process further comprises the step of seeding the crystallization mixture with a crystalline form of the compound of Formula (XIV) prior to performing constant volume distillation. In some embodiments, the process further comprises the step of seeding the crystallization mixture with a crystalline MeTHF solvate form of the compound of Formula (XIV) prior to performing constant volume distillation.

[0341] In some embodiments, the constant volume distillation is performed at a temperature below 45 °C. In some embodiments, the constant volume distillation is performed at a temperature between about 25 °C and about 30 °C.

[0342] In some embodiments, the process further comprises the step of isolating the crystalline form via filtration. In some embodiments, the process further comprises the step of washing the isolated crystalline form with MeTHF.

[0343] In another aspect, the disclosure provides a process for preparing a crystalline MTBE solvate form of the compound of Formula (XIV’), wherein the process comprises:

[0344] (1) suspending a compound of Formula (XIV’) in a first solvent comprising MeTHF; and

[0345] (2) adding a second solvent consisting of MTBE to provide the crystalline form.

[0346] In an embodiment, the disclosure provides a process for preparing a crystalline MTBE solvate form of the compound of Formula (XIV), wherein the process comprises: (1) suspending a compound of Formula (XIV) in a first solvent comprising MeTHF; and

[0347] (2) adding a second solvent consisting of MTBE to provide the crystalline form.

[0348] In some embodiments, step (1) comprises suspending a crystalline MeTHF solvate form of the compound of Formula (XIV) in the first solvent.

[0349] In some embodiments, the first solvent further comprises one or more of acetonitrile and water.

[0350] In some embodiments, the first solvent comprises at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% MeTHF by weight. In some embodiments, the first solvent comprises at least 95% MeTHF by weight.

[0351] In some embodiments, at least 5 L of the second solvent are added per mol of the compound of Formula (XIV). In some embodiments, at least 6 L of the second solvent are added per mol of the compound of Formula (XIV). In some embodiments, at least 7 L of the second solvent are added per mol of the compound of Formula (XIV). In some embodiments, at least 8 L of the second solvent are added per mol of the compound of Formula (XIV). In some embodiments, at least 9 L of the second solvent are added per mol of the compound of Formula (XIV).

[0352] In some embodiments, the second solvent is added over a period of at least 30 minutes. In some embodiments, the second solvent is added over a period of at least 1 hour. In some embodiments, the second solvent is added over a period of at least 2 hours.

[0353] In some embodiments, the process further comprises the step of isolating the crystalline form via filtration. In some embodiments, the process further comprises the step of washing the isolated crystalline form with MTBE.

[0354] In another aspect, the disclosure provides a process for preparing a crystalline EtOAc solvate form of the compound of Formula (XIV’), wherein the process comprises:

[0355] (1) forming a suspension of a compound of Formula (XIV’) in a first solvent comprising acetonitrile, EtOAc, and water; and

[0356] (2) adding a second solvent comprising EtOAc to provide the crystalline form.

[0357] In an embodiment, the disclosure provides a process for preparing a crystalline EtOAc solvate form of the compound of Formula (XIV), wherein the process comprises:

[0358] (1) forming a suspension of a compound of Formula (XIV) in a first solvent comprising acetonitrile, EtOAc, and water; and (2) adding a second solvent comprising EtOAc to provide the crystalline form.

[0359] In some embodiments, step (1) comprises forming a suspension of a crystalline form of the compound of Formula (XIV) in the first solvent. In some embodiments, step (1) comprises forming a suspension of a crystalline MTBE solvate form of the compound of Formula (XIV) in the first solvent.

[0360] In some embodiments, the first solvent comprises about 30% to about 50% acetonitrile by volume. In some embodiments, the first solvent comprises about 35% to about 45% acetonitrile by volume. In some embodiments, the first solvent comprises about 40% acetonitrile by volume.

[0361] In some embodiments, the first solvent comprises about 40% to about 60% EtOAc by volume. In some embodiments, the first solvent comprises about 45% to about 55% EtOAc by volume. In some embodiments, the first solvent comprises about 52% EtOAc by volume.

[0362] In some embodiments, the first solvent comprises about 1% to about 15% water by volume. In some embodiments, the first solvent comprises about 5% to about 10% water by volume. In some embodiments, the first solvent comprises about 7.5% water by volume.

[0363] In some embodiments, the process further comprises the step of stirring the crystallization mixture for at least 1 hour after adding the second solvent.

[0364] In some embodiments, the process further comprises the step of seeding the suspension with a crystalline form of the compound of Formula (XIV) prior to addition of the second solvent. In some embodiments, the process further comprises the step of seeding the suspension with a crystalline EtOAc solvate form of the compound of Formula (XIV) prior to addition of the second solvent.

[0365] In some embodiments, the second solvent consists of EtOAc.

[0366] In some embodiments, the second solvent is added in two portions.

[0367] In some embodiments, the volume of the second solvent is equivalent to or greater than the volume of the first solvent. In some embodiments, the volume of the second solvent is greater than the volume of the first solvent.

[0368] In some embodiments, addition of the second solvent provides a crystallization mixture comprising the compound of Formula (XIV), the first solvent, and the second solvent, wherein the crystallization mixture comprises at least 55% EtOAc by volume. In some embodiments, the crystallization mixture comprises at least 60% EtOAc by volume. In some embodiments, the crystallization mixture comprises at least 65% EtOAc by volume. In some embodiments, the crystallization mixture comprises at least 70% EtOAc by volume. In some embodiments, the crystallization mixture comprises at least 75% EtOAc by volume. In some embodiments, the crystallization mixture comprises about 77% EtOAc by volume.

[0369] In some embodiments, after addition of the second solvent, the crystallization mixture is stirred for at least one day. In some embodiments, after addition of the second solvent, the crystallization mixture is stirred for at least two days. In some embodiments, after addition of the second solvent, the crystallization mixture is stirred for at least three days.

[0370] In some embodiments, the process further comprises the step of isolating the crystalline form via filtration. In some embodiments, the process further comprises the step of washing the isolated crystalline form with EtOAc.

[0371] In some embodiments, the crystalline form of the compound of formula (XIV) ethyl acetate solvate is characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least one peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of formula (XIV) ethyl acetate solvate is characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least two peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of formula (XIV) ethyl acetate solvate is characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least three peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of formula (XIV) ethyl acetate solvate is characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least four peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of formula (XIV) ethyl acetate solvate is characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least five peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20.

[0372] Some embodiments relate to a process for preparing the crystalline form of the compound of formula (XIV), wherein the process comprises: (1) forming a suspension of a compound of Formula (XIV):

[0373] (XIV), in a first solvent; and (2) adding a second solvent to provide the crystalline form.

[0374] 15. Crystalline Form of a Compound of Formula (XV)

[0375] The present disclosure further provides crystalline forms of a compound of Formula (XV):

[0376] (XV), or a pharmaceutically acceptable salt or solvate thereof. The compound of Formula (XV) has an amino acid string of Ac-Pen* -Asn-Thr(tBu)- Trp(7Me)-Lys(Ac)-Pen*-Tyr(2-Boc-ea)-2Nal-THP-Glu(tBu)-Asn-3Pal-Sarc-NH2, wherein Pen* and Pen* form a disulfide bond.

[0377] Crystalline forms of the compound of Formula (XV) exhibits higher purity and ease of processibility than the amorphous counterparts. The crystalizing process described herein is suitable for the scale up of the peptide manufacture process and produces high level of purity of peptide compounds required for pharmaceutical manufacturing.

[0378] In some embodiments, the crystalline form of the compound of Formula (XV) has form A, as characterized as having an XRPD pattern as shown in FIG. 25 A. In some embodiments, the crystalline form of the compound of Formula (XV) has form B,as characterized as having an XRPD pattern as shown in FIG. 25B. In some embodiments, the crystalline form of the compound of Formula (XV) has form C, as characterized as having an XRPD pattern as shown in FIG. 25C. In some embodiments, the crystalline form of the compound of Formula (XV) has form D, as characterized as having an XRPD pattern as shown in FIG. 25D. In some embodiments, the crystalline form of the compound of Formula (XV) has form E, as characterized as having an XRPD pattern as shown in FIG. 25E. In some embodiments, the crystalline form of the compound of Formula (XV) has form F, as characterized as having an XRPD pattern as shown in FIG. 25F. In some embodiments, the crystalline form of the compound of Formula (XV) has form G, as characterized as having an XRPD pattern as shown in FIG. 25G.

[0379] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.2° 20.

[0380] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.2° 20.

[0381] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one peak selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20.

[0382] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20.

[0383] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 26.

[0384] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 26 ± 0.2° 20.

[0385] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 26 ± 0.2° 20.

[0386] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 14.1°, 16.6°, 17.5°, 18.1°, 18.3°, 18.7°, 19.2°, 21.2°, 21.8°, 22.5°, 23.1°, 23.4°, and 24.9° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 14.1°, 16.6°, 17.5°, 18.1°, 18.3°, 18.7°, 19.2°, 21.2°, 21.8°, 22.5°, 23.1°, 23.4°, and 24.9° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 14.1°, 16.6°, 17.5°, 18.1°, 18.3°, 18.7°, 19.2°, 21.2°, 21.8°, 22.5°, 23.1°, 23.4°, and 24.9° 26 ± 0.2° 26.

[0387] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.2° 26.

[0388] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.2° 20.

[0389] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one peak selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20.

[0390] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20.

[0391] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.2° 20.

[0392] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least ten peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 26 ± 0.2° 20.

[0393] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.4° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD patern comprising at least one, at least two, at least three, or at least four peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 20.

[0394] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD patern comprising peaks at 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.2° 26 .

[0395] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, at least five, at least six, at least seven, or at least eight peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.2° 26 . In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one peak selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 26 In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD patern further comprising at least two peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.2° 26 . In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD patern further comprising at least three peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.2° 26 . In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least four peaks selected from3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 20 . In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.2° 26 .

[0396] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD patern comprising at least six, at least seven, or at least eight, selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, or at least eight selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, or at least eight selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 20.

[0397] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 20.

[0398] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, or at least none peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20.

[0399] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20.

[0400] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one peak selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20.. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20.

[0401] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20.

[0402] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, at least four, at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least one, at least two, at least three, or at least four peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20.

[0403] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising peaks at 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20.

[0404] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one, at least two, at least three, at least four, or at least five peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least one peak selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 26 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least two peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least three peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least four peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern further comprising at least five peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 26 ± 0.2° 26.

[0405] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 26 ± 0.3° 26. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six, at least seven, at least eight, at least nine, or at least ten peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 26 ± 0.2° 20.

[0406] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 5.7°, 8.4°, 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least six peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20.

[0407] In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.4° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.3° 20. In some embodiments, the crystalline form of the compound of Formula (XV) is characterized as having an XRPD pattern comprising at least eight peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20.The crystalline form of the compound of Formula (XV), when prepared according to the methods described herein, is of particular utility in the synthesis of the compound of Formula (I). Specifically, the crystalline form produced has a desirable particle size distribution that makes it suitable for large scale synthesis. The large particle size of the crystalline form allows for rapid isolation of the product via filtration. A crystalline form having a smaller particle size would clog the filter during this step and would result in unsuitably slow filtration rates.

[0408] Accordingly, in some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size between about 10 pm and about 100 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size between about 15 pm and about 80 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size between about 20 pm and about 50 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size between about 25 pm and about 40 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size between about 25 pm and about 35 pm.

[0409] In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size that is greater than about 10 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size that is greater than about 15 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size that is greater than about 20 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size that is greater than about 25 pm. In some embodiments, the crystalline form of the compound of Formula (XV) has an average particle size that is about 30 pm.

[0410] 15.1. Processes for Preparing a Crystalline Form of the Compound of Formula (XV)

[0411] The present disclosure further provides processes for preparing a crystalline form of a compound of Formula (XV’).

[0412] R1-X3a-X4a-X5a-X6a-X7a-X8a-X9a-Xl Oa-Xl 1 a-Xl 2a-Xl 3a-Xl 4a-Xl 5a-Xl 6a-R4(XV’), or a pharmaceutically acceptable salt or solvate thereof, wherein R1is H, or Ci-20 alkanoyl;

[0413] R4is NHP1;

[0414] P1is an amino protecting group or H;

[0415] X3a is absent or any amino acid residue;

[0416] X4a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0417] X5a is Cit, Glu, Gly, substituted Gly, Leu, He, beta- Ala, Ala, Lys, Asn, Pro, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), Gin, Asp, or Cys;

[0418] X6a is Thr, Aib, Asp, Dab, Gly, Pro, Ser, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha- MeAsn, alpha-MeThr, alpha-MeSer, or Vai;

[0419] X7a is unsubstituted Trp, or Trp substituted with cyano, halo, alkyl, substituted or unsubstituted aryl, haloalkyl, hydroxy, or alkoxy;

[0420] X8a is Gin, alpha-Me-Lys, alpha-MeLeu, alpha-MeLys(Ac), beta-homoGln, Cit, Glu, Phe, Asn, Thr, Vai, Aib, alpha-MeGln, alpha-MeAsn, Lys(Ac), Dab(Ac), Dap(Ac), homo- Lys(Ac), INal, 2Nal, or Trp;

[0421] X9a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0422] XI Oa is unsubstituted Phe, or Phe substituted with halo, alkyl, haloalkyl, hydroxy, alkoxy, carboxy, carboxamido, 2-aminoethoxy, or 2-acetylaminoethoxy;

[0423] XI la is 2Nal, Phe(2-Me), Phe(3-Me), Phe(4-Me), Phe(3,4-dimethoxy), INal, unsubstituted Trp, or Trp substituted with cyano, halo, alkyl, haloalkyl, hydroxy, alkoxy;

[0424] XI 2a is 4-amino-4-carboxy -tetrahydropyran (THP), alpha-MeLys, alpha-MeLeu, alpha- MeArg, alpha-MePhe, alpha-MeLeu, alpha-MeAsn, alpha-MeTyr, Ala, cyclohexylAla, Lys, or Aib;

[0425] XI 3a is Aib, Glu, Cit, Gin, Lys(Ac), alpha-MeArg, alpha-MeGlu, alpha-MeLeu, alpha- MeLys, alpha-Me-Asn, alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), or Lys; or XI 3a is Lys, pegylated Lys, b-homoGlu, or Lys(Y2-Ac), wherein Y2 is an amino acid residue;

[0426] XI 4a is Asn, 2Nal, Aib, Arg, Cit, Asp, Phe, Gly, Lys, Leu, Ala, (D)Ala, beta- Ala, His, Thr, Gin, Ser, (D)Ser, Trp, alpha-MeGln, alpha-MeAsn, alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), or Lys(Ac); XI 5a is Ala, beta- Ala, Arg, Asn, Asp, Cit, Cys, Glu, Gin, Gly, substituted or unsubstituted His, (D)His, He, Leu, (D)Leu, Lys, (D)Lys, Met, 2Pal, 3Pal, or 4Pal, Phe, Pro, 5-Pyal, 2Quin, 3 Quin, Ser, Thr, Trp, Tyr, or Vai;

[0427] Xl 6a is absent or Sarc, aMeLeu, (D)NMeTyr, His, (D)Thr, beta- Ala, Pro, or (D)Pro; and the compound is cyclized via a disulfide or thioether bond between X4a and X9a; wherein the side chains of each of the amino acid residues are independently optionally protected by suitable protecting groups.

[0428] In some embodiments of the processes for preparing a crystalline form of the compound of Formula (XV’):

[0429] R1is H, or Ci-20 alkanoyl;

[0430] R4is NHP1;

[0431] P1is an amino protecting group or H;

[0432] X3a is absent or any amino acid residue;

[0433] X4a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0434] X5a is Cit, Glu, Gly, substituted Gly, Leu, He, beta- Ala, Ala, Lys, Asn, Pro, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), Gin, Asp, or Cys;

[0435] X6a is Thr, protected Thr, Aib, Asp, Dab, Gly, Pro, Ser, alpha-MeGln, alpha-MeLys, alpha-MeLeu, alpha- MeAsn, alpha-MeThr, alpha-MeSer, or Vai;

[0436] X7a is unsubstituted Trp, or Trp substituted with cyano, halo, alkyl, substituted or unsubstituted aryl, haloalkyl, hydroxy, or alkoxy;

[0437] X8a is Gin, alpha-Me-Lys, alpha-MeLeu, alpha-MeLys(Ac), beta-homoGln, Cit, Glu, Phe, Asn, Thr, Vai, Aib, alpha-MeGln, alpha-MeAsn, Lys(Ac), Dab(Ac), Dap(Ac), homo- Lys(Ac), INal, 2Nal, or Trp;

[0438] X9a is Abu, Cys, (D)Cys, alpha-MeCys, (D)Pen, or Pen;

[0439] XI 0a is unsubstituted Phe, or Phe substituted with halo, alkyl, haloalkyl, hydroxy, protected hydroxy, alkoxy, carboxy, protected carboxy, carboxamido, protected carboxamido, 2- aminoethoxy, protected 2-aminoethoxy, or 2-acetylaminoethoxy;

[0440] XI la is 2Nal, Phe(2-Me), Phe(3-Me), Phe(4-Me), Phe(3,4-dimethoxy), INal, unsubstituted Trp, or Trp substituted with cyano, halo, alkyl, haloalkyl, hydroxy, alkoxy; XI 2a is 4-amino-4-carboxy -tetrahydropyran (THP), alpha-MeLys, alpha-MeLeu, alpha- MeArg, alpha-MePhe, alpha-MeLeu, alpha-MeAsn, alpha-MeTyr, Ala, cyclohexylAla, Lys, or Aib;

[0441] XI 3a is Aib, Glu, protected Glu, Cit, Gin, Lys(Ac), alpha-MeArg, alpha-MeGlu, protected alpha-MeGlu, alpha-MeLeu, alpha-MeLys, alpha-Me-Asn, alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), or Lys; or XI 3a is Lys, pegylated Lys, b-homoGlu, or Lys(Y2-Ac), wherein Y2 is an amino acid residue;

[0442] XI 4a is Asn, 2Nal, Aib, Arg, Cit, Asp, Phe, Gly, Lys, Leu, Ala, (D)Ala, beta- Ala, His, Thr, Gin, Ser, (D)Ser, Trp, alpha-MeGln, alpha-MeAsn, alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), or Lys(Ac);

[0443] XI 5a is Ala, beta- Ala, Arg, Asn, Asp, Cit, Cys, Glu, Gin, Gly, substituted or unsubstituted His, (D)His, He, Leu, (D)Leu, Lys, (D)Lys, Met, 2Pal, 3Pal, or 4Pal, Phe, Pro, 5-Pyal, 2Quin, 3 Quin, Ser, Thr, Trp, Tyr, or Vai;

[0444] Xl 6a is absent or Sarc, aMeLeu, (D)NMeTyr, His, (D)Thr, beta- Ala, Pro, or (D)Pro; and the compound is cyclized via a disulfide bond between X4a and X9a; or the compound is cyclized via a thioether bond between X4a and X9a.

[0445] In some embodiments, X3a is absent

[0446] In some embodiments, X4a is Abu or Pen. In some embodiments, X4a is Pen.

[0447] In some embodiments, X5a is Cit, Glu, Gly, Leu, He, Ala, Lys, Asn, alpha-MeGln, alpha- MeLys, alpha-MeLeu, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo- Lys(Ac), Gin, or Asp. In some embodiments, X5a is Cit, Glu, Asn, alpha-MeGln, alpha-MeAsn, Lys(Ac), alpha-MeLys(Ac), Dab(Ac), Dap(Ac), homo-Lys(Ac), Gin, or Asp. In some embodiments, X5a is Asn.

[0448] In some embodiments, X6a is protected Thr. In some embodiments, X6a is Thr(tBu).

[0449] In some embodiments, X7a is Trp substituted with alkyl or substituted or unsubstituted aryl. In some embodiments, X7a is Trp(7Me).

[0450] In some embodiments, X8a is Gin, alpha-Me-Lys, alpha-MeLys(Ac), Asn, Aib, alpha- MeGln, alpha-MeAsn, Lys(Ac), Dab(Ac), Dap(Ac), or homo-Lys(Ac). In some embodiments, X8a is Gin, Lys(Ac), Dab(Ac), Dap(Ac), or homo-Lys(Ac). In some embodiments, X8a is Lys(Ac)). In some embodiments, X9a is Cys, alpha-MeCys, or Pen. In some embodiments, X9a is Pen.

[0451] In some embodiments, XI Oa is Phe substituted with protected 2-aminoethoxy. In some embodiments, XI Oa is Tyr(2-Boc-ea).

[0452] In some embodiments, XI la is 2Nal, INal, or Trp substituted with cyano, halo, alkyl, haloalkyl, hydroxy, alkoxy. In some embodiments, XI la is 2Nal.

[0453] In some embodiments, XI 2a is THP, alpha-MeLys, alpha-MeLeu, cyclohexylAla, or Aib. In some embodiments, XI 2a is THP.

[0454] In some embodiments, XI 3a is protected Glu or Lys(Ac). In some embodiments, XI 3a is Glu(tBu) or Lys(Ac). In some embodiments, XI 3a is Glu(tBu).

[0455] In some embodiments, XI 4a is Asn.

[0456] In some embodiments, XI 5a is His, He, Leu, 2Pal, 3Pal, or 4Pal, Phe, 5-Pyal, 2Quin, or 3Quin. In some embodiments, XI 5a is 3Pal.

[0457] In some embodiments, XI 6a is absent or Sarc. In some embodiments, XI 6a is absent. In some embodiments, XI 6a is Sarc.

[0458] In some embodiments, the compound of Formula (XV’) is a compound of Formula (XV):

[0459] (XV).

[0460] Accordingly, the present disclosure further provides processes for preparing a crystalline form of the compound of Formula (XV). In an aspect, the disclosure provides a process for preparing a crystalline form of a compound of Formula (XV’), wherein the process comprises:

[0461] (1) dissolving a compound of Formula (XV’) in a first solvent comprising an alcohol and adding a second solvent comprising water to form a crystallization mixture;

[0462] (2) adjusting the temperature of the crystallization mixture to a first temperature;

[0463] (3) decreasing the temperature of the crystallization mixture to a second temperature, wherein the second temperature is lower than the first temperature;

[0464] (4) repeating steps (2)-(3) at least once to provide the crystalline form.

[0465] In an embodiment, the disclosure provides a process for preparing a crystalline form of a compound of Formula (XV), wherein the process comprises:

[0466] (1) dissolving a compound of Formula (XV) in a first solvent comprising an alcohol and adding a second solvent comprising water to form a crystallization mixture;

[0467] (2) adjusting the temperature of the crystallization mixture to a first temperature;

[0468] (3) decreasing the temperature of the crystallization mixture to a second temperature, wherein the second temperature is lower than the first temperature;

[0469] (4) repeating steps (2)-(3) at least once to provide the crystalline form.

[0470] In some embodiments, the alcohol is MeOH or 2-propanol. In some embodiments, the alcohol is MeOH. In some embodiments, the alcohol is 2-propanol.

[0471] In some embodiments, the first solvent comprises at least about 80% of the alcohol by volume. In some embodiments, the first solvent comprises at least about 85% of the alcohol by volume. In some embodiments, the first solvent comprises at least about 90% of the alcohol by volume. In some embodiments, the first solvent comprises at least about 95% of the alcohol by volume.

[0472] In some embodiments, the second solvent is an aqueous solvent. In some embodiments, the second solvent is purified water. In some embodiments, the second solvent is an aqueous solution of ammonium acetate. In some embodiments, the second solvent is 1.6 M ammonium acetate.

[0473] In some embodiments, the compound of Formula (XV) is dissolved in the first solvent at a temperature between about 30 °C and about 40 °C.

[0474] In some embodiments, prior to step (2), the crystallization mixture is seeded with a crystalline form of the compound of Formula (XV). In some embodiments, prior to step (2), the crystallization mixture is seeded with a slurry comprising a crystalline form of the compound of Formula (XV).

[0475] In some embodiments, the first temperature is between about 10 °C and about 30 °C. In some embodiments, the first temperature is between about 15 °C and about 25 °C. In some embodiments, the first temperature is about 20 °C.

[0476] In some embodiments, the second temperature is between about -10 °C and about 10 °C. In some embodiments, the second temperature is between about 0 °C and about 10 °C. In some embodiments, the second temperature is about 5 °C.

[0477] In some embodiments, step (4) comprises repeating steps (2)-(3) at least two times. In some embodiments, step (4) comprises repeating steps (2)-(3) at least three times.

[0478] In some embodiments, the process further comprises the step of isolating the crystalline form via filtration. In some embodiments, the process further comprises the step of washing the isolated crystalline form with an alcohol, water, or a combination thereof. In some embodiments, the process further comprises the step of washing the isolated crystalline form with a mixture of 2-propanol and water (e.g., a 5: 11 v / v mixture). Each embodiment of the present disclosure defined in this or in any other section may incorporate definitions and limitations, such as those set forth throughout the originally filed disclosure, specification, and claims.

[0479] Examples

[0480] Abbreviations

[0481] Herein and throughout the application, the following abbreviations may be used.

[0482] Ac acetyl

[0483] Acm acetamidomethyl

[0484] ACN or MeCN acetonitrile

[0485] Boc or BOC / c / 7-butyloxy carbonyl

[0486] Bz benzoyl

[0487] Cbz or Z benzyloxy carbonyl

[0488] DCM dichloromethane

[0489] Et ethyl

[0490] EtOAc ethyl acetate EtOH ethanol

[0491] Fmoc 9-fluorenylmethoxy carbonyl

[0492] IPA isopropyl alcohol

[0493] IPAc isopropylacetate

[0494] Me methyl

[0495] MeOH methanol

[0496] MeTHF 2-methyltetrahydrofuran

[0497] MTBE methyl / c / 7-butylether

[0498] Mtt 4-methyltrityl

[0499] NMP N-methyl-2-pyrrolidone

[0500] 1-PrOH 1 -propanol

[0501] 2-PrOH 2-propanol rt or RT room temperature tBu tert-butyl

[0502] THF tetrahydrofuran

[0503] Trt trityl v / v volume for volume w / w weight for weight

[0504] XRPD X-Ray powder diffraction

[0505] Structures of non-naturally occurring amino acids mentioned throughout the present disclosure are provided in Table C.

[0506] Table C:

[0507] Example 1: Preparation of a Crystalline Form of a Compound of Formula (II)

[0508] Crystallization protocol'. To a solution of crude compound of Formula (II) in MeCN was added seeding material, and the mixture was stirred at 0 °C for 12 hours. The mixture was warmed up to 20 °C over 1 hour, and the slurry was allowed to stand for a further 4 hours at 20 °C. Water was then added dropwise over 2 hours at 20 °C, and the slurry was allowed to stand for another 4 hours at 20 °C. The slurry was then filtered, and the solid was washed with a mixture of MeCN and water (1:1 v / v). The product was then dried in vacuo. Example 2: Preparation of a Crystalline Form of a Compound of Formula (III)

[0509] Crystallization protocol'. To a solution of crude compound of Formula (III) in MeTHF was added seeding material (as slurry), and the mixture was stirred at 5 °C for 20 hours. Then, MTBE was added over 5 hours, and the mixture was stirred at 5 °C for 4 hours. The temperature was adjusted to 20 °C and stirred for 8 hours. The mixture was then filtered, and the solid was washed with a mixture of cold MeTHF and MTBE (1:2 v / v). The product was then dried at 25 Example 3: Preparation of a Crystalline Form of a Compound of Formula (IV)

[0510] Crystallization protocol'. To a solution of crude compound of Formula (IV) in IP Ac was added n-heptane dropwise over 5 hours at 25 to 35 °C. The mixture was cooled to -5 to 5 °C over 5 hours and then stirred at that temperature for 6 hours. The mixture was then filtered, and the solid was washed with a mixture of cold IP Ac and n-heptane (1:2.5 v / v). The product was then dried in vacuo.

[0511] Example 4: Preparation of a Crystalline Form of a Compound of Formula (V)

[0512] Crystallization protocol'. To a solution of crude compound of Formula (V) in MeTHF was added EtOH dropwise over 7 hours at 15 to 25 °C. The mixture was stirred for 3 hours at this temperature. Then, the mixture was cooled to -5 to 5 °C over 6 hours and then stirred at that temperature for 16 hours. The mixture was then filtered, and the solid was washed with a mixture of cold EtOH and MeTHF (4: 1 v / v). The product was then dried in vacuo.

[0513] Example 5: Preparation of a Crystalline Form of a Compound of Formula (VI)

[0514] Crystallization protocol'. To a solution of crude compound of Formula (VI) in MeTHF was added seeding material. The mixture was stirred for 1 hour at a temperature below 40 °C, and then MeCN was added over 5 hours. The mixture was then stirred for 2 hours. The temperature was adjusted to 0 °C, and the mixture was stirred for an additional 9 hours. The mixture was then filtered, and the solid was washed with a mixture of MeTHF and MeCN (1:2 v / v). The product was then dried in vacuo.

[0515] Example 6: Preparation of a Crystalline Form of a Compound of Formula (VII)

[0516] Crystallization protocol'. To a suspension of crude compound of Formula (VII) in NMP was added EtOAc over 7 hours at 20-30 °C. The temperature was adjusted to about 15 °C over 1 hour, and the mixture was stirred at this temperature for 7 hours. The mixture was then filtered, and the solid was washed with EtOAc. The product was then dried in vacuo. Example 7: Preparation of a Crystalline Form of a Compound of Formula (IX)

[0517] Crystallization protocol'. Crude compound of Formula (IX) was suspended in MTBE to form a slurry. The slurry was stirred for 4 hours at 20 °C. The mixture was then filtered, and the solid was washed with MTBE. The product was then dried in vacuo.

[0518] Example 8: Preparation of a Crystalline Form of a Compound of Formula (X)

[0519] Crystallization protocol'. Crude compound of Formula (X) was suspended in EtOH, and the mixture was stirred at about 50 °C for an hour to obtain a clear solution. The temperature of the solution was adjusted to about 40 °C before addition of seeding material. The mixture was then stirred at 40 °C for 3 hours. An additional portion of EtOH was added over 5 hours at 40 °C, and then the mixture was stirred at that temperature for 2 hours. The temperature was adjusted to 20 °C over 3 hours and stirred for 3 hours. Then the mixture was warmed to 50 °C over 1.5 hours and stirred for 8 hours. The mixture was again cooled to 20 °C over 3 hours and stirred for 4 hours before cooling to 10 °C over 3 hours and stirring for a final 10 hours. The mixture was then filtered, and the solid was washed with EtOH. The product was then dried in vacuo.

[0520] Example 9: Preparation of a Crystalline Form of a Compound of Formula (XI)

[0521] Crystallization protocol'. Crude compound of Formula (XI) was suspended in MeCN, and the temperature was adjusted to about 10 °C before the addition of seeding material. The mixture was stirred for 8 hours before the addition of 5% NaHSO4 aq. solution over 14 hours. The mixture was then stirred at 10 °C for an additional 5 hours before filtering the suspension and washing the solid with water. The solid was then resuspended in DCM and stirred at about 25 °C for 5 hours. The mixture was then filtered, and the solid was washed with DCM. The product was then dried in vacuo.

[0522] Example 10: Preparation of a Crystalline Form of a Compound of Formula (XII)

[0523] Crystallization protocol'. Crude compound of Formula (XII) was suspended in MeTHF before the addition of seeding material and MeCN. The mixture was stirred at 25 °C for 3 hours before distilling under vacuum (temperature kept below 40 °C). An additional portion of MeCN was added, and the mixture was then stirred at 40 °C for 2 hours. The temperature was reduced to 20 °C over 4 hours, and the mixture was stirred at this temperature for 15 hours. The mixture was then filtered, and the solid was washed with MeCN. The product was then dried in vacuo.

[0524] Example 11: Preparation of a Crystalline Form of a Compound of Formula (XIII)

[0525] Crystallization protocol'. A suspension of crude compound of Formula (XIII) in a mixture of MeCN and water (9: 1) was allowed to stand before isolating the solid product.

[0526] Characterization'. An XRPD pattern of the solid confirmed its crystallinity (FIG. 20). The following peaks were observed: 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.2° 20.

[0527] Example 12: Preparation of a Crystalline MeTH F Solvate Form of a Compound of Formula (XIV)

[0528] Crystallization protocol. Crude compound of Formula (XIV) was suspended in a solution of acetonitrile and water. Distillation was performed on the mixture (200 mbar; 26.5-28.4 °C) with addition of MeTHF to maintain constant volume. Distillation proceeded for 30 minutes and was stopped when 80 mL of MeTHF had been added. The solid was isolated by filtration and washed with MeTHF. The solid was then dried in vacuo.

[0529] Characterization'. An XRPD pattern of the solid confirmed its crystallinity (FIG. 21). The following peaks were observed: 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.2° 20.

[0530] Example 13: Preparation of a Crystalline MTBE Solvate Form of a Compound of Formula (XIV)

[0531] Crystallization protocol. The crystalline MeTHF solvate of the compound of Formula (XIV) (as prepared in Example 12) was suspended in MeTHF (14.7 L / mol). The temperature was adjusted to 25 °C, and the mixture was stirred for 4 hours. MTBE (9.32 L / mol) was added over 2 hours, and the resulting mixture was stirred for at least 1 hour. The resulting solid was isolated by filtration and washed with MTBE.

[0532] Characterization'. An XRPD pattern of the solid confirmed its crystallinity (FIG. 22). The following peaks were observed: 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.2° 20. Alternate crystallization protocol: To a solution of crude compound of Formula (XIV) in 2-MeTHF (17.5 L / mol) was added 2-MeTHF (27.9 L / mol). The temperature was adjusted to 25 °C and the mixture was stirred for 4 hr. MTBE (9.3 L / mol) was then dosed over 30 minutes and the resulting mixture was stirred for 1 hr. Compound of Formula (XIV) was isolated as MTBE solvate wet cake. This MTBE solvate wet cake was then used in the crystallization procedure described in Example 14.

[0533] Example 14A: Preparation of a Crystalline EtOAc Solvate Form of a Compound of Formula (XIV)

[0534] Seeding material. The seeding material used was a crystalline EtOAc solvate of the compound of Formula (XIV) having the following XRPD peaks: 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20.

[0535] Crystallization protocol. The crystalline MTBE solvate of the compound of Formula (XIV) (as prepared in Example 13) was suspended in a mixture of MeCN (3.54 L / mol), EtOAc (4.51 L / mol), and purified water (0.65 L / mol) at 20 °C, while stirring. To the mixture was added EtOAc (3.21 L / mol) over 15 minutes at 20 °C. To this mixture was added seeding material before stirring for a minimum of 30 minutes. Afterward, an additional portion of EtOAc (6.41 L / mol) was added over 240 minutes. The mixture was then stirred for 3 days at 20 °C. The resulting solid was then isolated via filtration and washed with EtOAc. The solid was then dried in vacuo.

[0536] Characterization'. An XRPD pattern of the solid confirmed its crystallinity (FIG. 23). The following peaks were observed: 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20.

[0537] Example 14B: Direct preparation of a Crystalline EtOAc Solvate Form of a Compound of Formula (XIV)

[0538] Seeding material. The seeding material used was a crystalline EtOAc solvate of the compound of Formula (XIV) having the following XRPD peaks: 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 5 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20. Crystallization protocol'. A solution crude compound of Formula (XIV) in a mixture of EtOAc, water and acetonitrile was distilled to afford a final 8 volume solution. The solvent composition was adjusted to make a mixture of MeCN (2.82 volumes), water (0.51 volumes, ± 0.49 volumes) and ethyl acetate (6.16 volumes). The mixture was seeded with pure compound of Formula (XIV) EtOAc solvate and aged for 1 hour. EtOAc (11.5 volumes) was added over 6 hours and the solution was aged for up to 72 h at 20 °C. The resulting solid was then isolated via filtration and washed with EtOAc. The solid was then dried in vacuo.

[0539] Characterization'. An XRPD pattern of the solid confirmed its crystallinity (FIG. 23). The following peaks were observed: 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.2° 20.

[0540] Example 15: Purity of Crystalline Forms of a Compound of Formula (XIV)

[0541] The purities of the crystalline MeTHF, MTBE, and EtOAc solvate forms of the compound of Formula (XIV) prepared according to the methods described in Examples 12-14 are presented in Table D. Notably, the crystalline EtOAc solvate form was isolated with exceptionally high purity, making it a particularly useful intermediate in the preparation of the compound of Formula (I).

[0542] Table D. Purity of Crystalline Forms of a Compound of Formula (XIV)

[0543] Example 16: Preparation of a Crystalline Form of a Compound of Formula (XV)

[0544] Seeding material'. The seeding material used was a slurry of a crystalline form of the compound of Formula (XV) having the following XRPD peaks: 5.2°, 6.1°, 8.8°, 10.2°, 13.7°, 16.0°, 19.5°, and 25.1° 26 ± 0.4° 20. Crystallization protocol'. Crude compound of Formula (XV) was dissolved in methanol (10-16 wt / wt%) at 40 °C before the addition of 1.6M ammonium acetate to achieve a water content of 15-20 wt / wt%. The temperature of the mixture was adjusted to 35 °C before addition of seeding material. The resulting slurry was stirred for 8 hours at 35 °C and then cooled to -5 °C over 16 hours. The slurry was then stirred at -5 °C for at least 5 hours. The solid product was then isolated via filtration and washed with a mixture of water and methanol (1: 1 v / v). ). This provided compound of Formula (XV) (Wet solid material) as shown in XRPD pattern in Figure 25B. The product was then dried in vacuo. This provided compound of Formula (XV) (Dry solid material) as shown in XRPD pattern in Figure 25C.

[0545] Characterization'. An XRPD pattern (as shown on Figure 25B) of the wet solid confirmed its crystallinity. The following peaks were observed: 5.2°, 6.1°, 8.8°, 10.2°, 13.7°, 16.0°, 19.5°, and 25.1° 20 ± 0.4° 20. An XRPD pattern (as shown on Figure 25C) of the dry solid confirmed its crystallinity. The following peaks were observed: 6.2°, 7.6°, 8.8°, 10.5°, 13.0°, and 16.2° 20 ± 0.4° 20.

[0546] Example 17A: Alternate Preparation of a Crystalline Form of a Compound of Formula (XV)

[0547] Seeding material'. The seeding material used was a slurry of a crystalline form of the compound of Formula (XV) having the following XRPD peaks: 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.2° 20.

[0548] Crystallization protocol'. Crude compound of Formula (XV) was dissolved in 2-pr opanol (11.68 L / mol), and the temperature was adjusted to 30 °C before the addition of purified water (4.95 L / mol) over 1 hour. The temperature of the mixture was adjusted to 20 °C over 15 minutes before the addition of seeding material (0.01 mol / mol). The resulting mixture was stirred for 8 hours at 20 °C and then cooled to 5 °C over 8 hours. The temperature was then raised to 20 °C over 1 hour. The temperature was then decreased to 5 °C over 8 hours and increased to 20 °C over 1 hour two more times before the addition of more purified water (16.9 L / mol) over 9 hours. The mixture was then stirred for 8 more hours at 20 °C before collecting the product via filtration and washing with a mixture of 2-propanol and purified water (5: 11 v / v). The product was then dried in vacuo.

[0549] Characterization'. An XRPD pattern of the solid confirmed its crystallinity (FIG. 25 A). The following peaks were observed: 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 26 ± 0.2° 20.

[0550] Example 17B: Alternate Preparation of a Crystalline Form of a Compound of Formula (XV)

[0551] Seeding material'. The seeding material used was a slurry of a crystalline form of the compound of Formula (XV) having the following XRPD peaks: 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 20 or a slurry of a crystalline form of the compound of Formula (XV) (10-50 w / w%) in isopropanol / water mixture (1 / 2 v / v) having the following XRPD peaks: 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20.

[0552] Crystallization protocol'. Crude compound of Formula (XV) was dissolved in 2-propanol (11.68 L / mol), and the temperature was adjusted to 30 °C before the addition of purified water (4.95 L / mol) over 1 hour. The temperature of the mixture was adjusted tol8 °C - 20 °C over 15 minutes before the addition of seeding material (0.005-0.05 mol / mol). The resulting mixture was stirred for 8 hours at 18 °C - 20 °C and then cooled to 5 °C over 8 hours. The temperature was then raised to 18 °C - 20 °C over 1 hour. The temperature was then decreased to 5 °C over 8 hours and increased to 18 °C - 20 °C over 1 hour two more times before the addition of more purified water (16.9 L / mol) over 9 hours. The mixture was then stirred for 8 more hours at 18 °C - 20 °C before collecting the product via filtration and washing with a mixture of 2-propanol and purified water (5: 11 v / v). An XRPD pattern (as shown on Figure 25D) of the wet solid confirmed its crystallinity. The wet solid crystalline material has the following characteristic XRPD peaks: 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.2° 20.

[0553] The product was then dried in vacuo. An XRPD pattern (as shown on Figure 25E) of the solid confirmed its crystallinity. The dry crystalline material has the following characteristic XRPD peaks: 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.2° 26 Example 17C: Alternate Preparation of a Crystalline Form of a Compound of Formula

[0554] (XV)

[0555] Crystallization protocol'. Crude compound of Formula (XV) was charged in the reactor followed by 5 v / w of 2-propanol and 0.5 v / w of purified water. The mixture was stirred at 20°C for 30 min before addition of 5.5 v / w of purified water over 1 h under vigorous stirring. Additional 5 v / w of purified water were added over 4h at 20°C. The mixture was then stirred for 11 more hours at 20 °C before collecting the product via filtration. An XRPD pattern (as shown on Figure 25F) of the solid confirmed its crystallinity. The filtered crystalline material had the following XRPD peaks: 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.2° 20.

[0556] The product was then dried in vacuo. An XRPD pattern (as shown on Figure 25G) of this dry solid confirmed its crystallinity. The filtered crystalline material has the following XRPD peaks 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 20 ± 0.2° 20.

[0557] Particle Size and Filtration: The average particle size of the crystalline product of compound of Formula (XV) was determined to be about 33 pm (FIG. 26). The large particle size of the product allowed for rapid isolation of the crystals via filtration, as shown in FIG. 27, which shows a 2 minute filtration time for 400 mL on a 20 cm2filter (approximately 3000 L / m2*h) (Ln(cake resistance: 22.7; compressibility: 0.9).

[0558] Example 17D: Alternate Preparation of a Crystalline Form of a Compound of Formula (XV)

[0559] Crystallization protocol'. EtOH solution of the compound of formula (XV) in 5 Vol. concentration at 35 deg C was added slowly to 10 Vol. of water at 35 deg C containing 0.7% of crystalline seed in suspension. The mixture was continuously stirred during addition of the EtOH solution to the antisolvent, water. The suspension was aged for some hours before slow cooling to 0 deg C, aged at 0 deg C, and filtered, and the product is then dried by vacuum at 40 deg C. The crystalline material was characterized as an ethanol solvate of the compound of formula (XV). The crystalline material had the following XRPD peaks: 4.9°, 5.6°, 6.8°, 9.8°, 10.1°, 10.9°, 11.2°, 11.8°, 12.7°, 13.0°, 13.4°, 14.1°, 4.7°, 14.9°, 15.5°, 16.0°, 16.2°, 16.7°, 17.1°, 17.4°, 17.6°, 18.3°, 18.7°, 19.1°, 19.4°, 19.6°, 19.9°, 20.1°, 20.8°, 20.9°, 21.3°, 22.0°, 22.6°, 22.9°, 23.2°, 23.6°, 24.1°, 24.5°, 25.2°, 25.5°, 26.5°, 27.0°, 28.3°, 28.9°, 30.1°, 30.4°, 31.4°, 32.0°, 32.8°, 33.9°, 34.5 ± 0.2° 26.

[0560] Although the foregoing disclosure has been described in some detail by way of illustration and example for purposes of clarity of understanding, one of skill in the art will appreciate that certain changes and modifications can be practiced within the scope of the appended claims. It is to be understood that the present disclosure is not limited to the aspects and embodiments illustrated herein above and the right is reserved to the illustrated aspects and all modifications coming within the scope of the claims.

Claims

CLAIMS1. A crystalline form of a compound of Formula (XIV):(XIV), or a pharmaceutically acceptable salt or solvate thereof.

2. The crystalline form of claim 1 , wherein the crystalline form is a solvate.

3. The crystalline form of claim 2, wherein the solvate of the crystalline form is selected from the group consisting of an ethyl acetate (EtOAc) solvate, a methyl tert-butyl ether (MTBE) solvate, an 2-methyltetrahydrofuran (MeTHF) solvate and an acetonitrile (MeCN) solvate.

4. The crystalline form of claims 1-3, wherein the crystalline form is an ethyl acetate (EtOAc) solvate.

5. The crystalline form of claims 1- 4, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least two peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20.

6. The crystalline form of claims 1- 5, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least three peaks selected from 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 26 ± 0.4° 20.

7. The crystalline form of claim 1 or claim 4, characterized as having an X-ray powder diffraction (XRPD) pattern comprising peaks at 6.2°, 10.7°, 13.5°, 15.7°, 16.5°, and 17.3° 20 ± 0.4° 20.

8. The crystalline form of claim 7, characterized as having an XRPD pattern further comprising at least one peak selected from 7.4°, 8.0°, 10.2°, 11.1°, 11.9°, 12.4°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 26 ± 0.4° 20.

9. The crystalline form of claims 1-2 or claims 7-8, characterized as having an XRPD pattern comprising peaks at 6.2°, 7.4°, 8.0°, 10.2°, 10.7°, 11.1°, 11.9°, 12.4°, 13.5°, 15.7°, 16.5°, 17.3°, 18.8°, 19.5°, 20.2°, 21.1°, and 22.2° 20 ± 0.4° 20.

10. The crystalline form of claim 1 or claim 4, characterized as having a XRPD pattern substantially as shown in FIG. 23.

11. The crystalline form of claims 1-3, wherein the crystalline form is a methyl tert- butyl ether (MTBE) solvate.

12. The crystalline form of claims 1- 3 or 11, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least one peaks selected from 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.4° 20.

13. The crystalline form of claims 1- 3 or 11-12, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least two peaks selected from 4.8°, 14.3°, 19.9°, and 20.8° 20 ± 0.4° 26.

14. The crystalline form of claims 1- 3 or 11-13, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least three peak selected from 4.8°, 14.3°, 19.9°, and 20.8° 26 ± 0.4° 26.

15. The crystalline form of claims 1-3 or claims 11-14, characterized as having an XRPD pattern comprising peaks at 4.8°, 14.3°, 19.9°, and 20.8° 26 ± 0.4° 26.

16. The crystalline form of claims 11-15 , characterized as having an XRPD pattern further comprising at least one peak selected from 5.8°, 11.6°, 15.5°, 17.9°, 22.0°, and 24.9° 26 ± 0.4° 20.

17. The crystalline form of any one of claims 1-3, and 11-16, characterized as having an XRPD pattern comprising peaks at 4.8°, 5.8°, 11.6°, 14.3°, 15.5°, 17.9°, 19.9°, 20.8°, 22.0°, and 24.9° 20 ± 0.4° 26.

18. The crystalline form of claims 1-3 or claims 11-17, characterized as having a XRPD pattern substantially as shown in FIG. 22.

19. The crystalline form of claims 1-3, wherein the crystalline form is a 2- methyltetrahydrofuran (MeTHF) solvate.

20. The crystalline form of claims 1- 3 or 19, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least one peak selected from 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20.

21. The crystalline form of claims 1- 3 or 19-20, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least two peaks selected from 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20.

22. The crystalline form of claims 1- 3 or 19-21, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least three peaks selected from 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20.

23. The crystalline form of claims 1-3 or claims 19-22, characterized as having an XRPD pattern comprising peaks at 6.0°, 6.8°, 11.2°, and 17.9° 20 ± 0.4° 20.

24. The crystalline form of claim 23, characterized as having an XRPD pattern further comprising at least one peak selected from 4.6°, 12.2°, 14.4°, 15.6°, 16.3°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20.

25. The crystalline form of any one of claims 1-3 and 19-24, characterized as having an XRPD pattern comprising peaks at 4.6°, 6.0°, 6.8°, 11.2°, 12.2°, 14.4°, 15.6°, 16.3°, 17.9°, 19.0°, 19.8°, and 24.6° 20 ± 0.4° 20.

26. The crystalline form of claims 1-3 or claims 19-25, characterized as having a XRPD pattern substantially as shown in FIG. 21.

27. The crystalline form of claims 1-3, wherein the crystalline form is an acetonitrile solvate.

28. The crystalline form of claims 1- 3 or 27, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least one peak selected from 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 2029. The crystalline form of claims 1- 3 or 27-28, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least two peaks selected from 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 2030. The crystalline form of claims 1- 3 or 27-29, characterized as having an X-ray powder diffraction (XRPD) pattern comprising at least three peaks selected from 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 20.

31. The crystalline form of claim 1 or claim 27, characterized as having an XRPD pattern comprising peaks at 6.4°, 13.9°, 16.6°, and 17.4° 20 ± 0.4° 20.

32. The crystalline form of claim 31, characterized as having an XRPD pattern further comprising at least one peak selected from 7.5°, 11.0°, 11.3°, 12.8°, 15.8°, 22.4°, 22.9°, and 23.8° 26 ± 0.4° 20.

33. The crystalline form of any one of claims 1, 27, or 31-32, characterized as having an XRPD pattern comprising peaks at 6.4°, 7.5°, 11.0°, 11.3°, 12.8°, 13.9°, 15.8°, 16.6°, 17.4°, 22.4°, 22.9°, and 23.8° 20 ± 0.4° 20.

34. The crystalline form of claim 1 or claim 27, characterized as having a XRPD pattern substantially as shown in FIG. 24.

35. A process for preparing the crystalline form of any one of claims 1-34, wherein the process comprises:(1) forming a suspension of a compound of Formula (XIV):(XIV), in a first solvent; and (2) adding a second solvent to provide the crystalline form.

36. A process for preparing the crystalline form of any one of claims 2-10 and 35, wherein the process comprises:(1) forming a suspension of a compound of Formula (XIV):(XIV), in a first solvent comprising acetonitrile, EtOAc, and water; and(2) adding a second solvent comprising EtOAc to provide the crystalline form.

37. The process of claim 36, wherein step (1) comprises forming a suspension of a crystalline form of the compound of Formula (XIV) in the first solvent.

38. The process of claim 37, wherein step (1) comprises forming a suspension of a crystalline MTBE solvate form of the compound of Formula (XIV) in the first solvent.

39. The process of any one of claims 35-38, wherein the first solvent comprises:30% to 50% acetonitrile by volume;40% to 60% EtOAc by volume; and1% to 15% water by volume.

40. The process of any one of claims 35-39, further comprising the step of seeding the suspension with a crystalline form of the compound of Formula (XIV) prior to addition of the second solvent.

41. The process of claim 40, further comprising the step of seeding the suspension with a crystalline EtOAc solvate form of the compound of Formula (XIV) prior to addition of the second solvent.

42. The process of any one of claims 35-41, wherein the second solvent consists of EtOAc.

43. The process of any one of claims 35-42, wherein the second solvent is added in two portions.

44. The process of any one of claims 35-43, wherein the volume of the second solvent is equivalent to or greater than the volume of the first solvent.

45. The process of any one of claims 35-44, wherein addition of the second solvent provides a crystallization mixture comprising the compound of Formula (XIV), the first solvent, and the second solvent, wherein the crystallization mixture comprises at least 65% EtOAc by volume.

46. The process of any one of claims 35-45, wherein after addition of the second solvent, the crystallization mixture is stirred for at least two days.

47. The process of any one of claims 35-46, further comprising the step of isolating the crystalline form via filtration and washing the crystalline form with EtOAc.

48. A process for preparing the crystalline form of any one of claims 11-18, wherein the process comprises:(1) suspending a compound of Formula (XIV):(XIV), in a first solvent comprising MeTHF; and(2) adding a second solvent consisting of MTBE to provide the crystalline form.

49. The process of claim 48, wherein the first solvent further comprises one or more of acetonitrile and water.

50. The process of claim 48 or claim 49, wherein the first solvent comprises at least 95% MeTHF by weight.

51. The process of any one of claims 48-50, wherein at least 7 L of the second solvent are added per mol of the compound of Formula (XIV).

52. The process of any one of claims 48-51, wherein the second solvent is added over a period of at least 30 minutes.

53. The process of any one of claims 48-52, wherein the second solvent is added over a period of at least 2 hours.

54. The process of any one of claims 48-53, further comprising the step of isolating the crystalline form via filtration and washing the crystalline form with MTBE.

55. A process for preparing the crystalline form of any one of claims 19-26, wherein the process comprises:(1) suspending a compound of Formula (XIV):(XIV), in a solvent comprising acetonitrile and water to form a crystallization mixture; and(2) performing constant volume distillation on the crystallization mixture by adding MeTHF at approximately the rate of distillation to form the crystalline form.

56. The process of claim 55, wherein the solvent further comprises sodium bisulfate.

57. The process of claim 55 or claim 56, wherein the solvent has a pH between about 2.5 and about 3.5.

58. The process of any one of claims 55-57, further comprising the step of seeding the crystallization mixture with a crystalline form of the compound of Formula (XIV) prior to performing constant volume distillation.

59. The process of claim 58, further comprising the step of seeding the crystallization mixture with a crystalline MeTHF solvate form of the compound of Formula (XIV) prior to performing constant volume distillation.

60. The process of any one of claims 55-59, wherein the constant volume distillation is performed at a temperature below 45 °C.

61. The process of any one of claims 55-60, wherein the constant volume distillation is performed at a temperature between about 25 °C and about 30 °C.

62. The process of any one of claims 55-61, further comprising the step of isolating the crystalline form via filtration and washing the crystalline form with MeTHF.

63. A crystalline form of a compound of Formula (XV):(XV), or a pharmaceutically acceptable salt or solvate thereof.

64. A crystalline form of a compound of Formula (XV):(XV), or solvate thereof.

65. The crystalline form of claim 63 or claim 64, characterized as having a XRPD pattern substantially as shown in FIG. 25A, FIG. 25B, FIG. 25C, FIG. 25D, FIG. 25E, FIG. 25F, or FIG. 25G.

66. The crystalline form of claims 63-64, having an average particle size of between about 20 pm and about 50 pm.

67. The crystalline form of claim 66, having an average particle size of between about 25 pm and about 40 pm.

68. The crystalline form of claim 67, having an average particle size greater than about 20 pm.

69. The crystalline form of any one of claims 63-68, characterized as having an XRPD pattern comprising at least one peaks selected from 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.4° 20.

70. The crystalline form of any one of claims 63-69, characterized as having an XRPD pattern comprising at least three peaks selected from 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.4° 20.

71. The crystalline form of any one of claims 63-70, characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 11.7°, 13.9°, and 16.6° 20 ± 0.4° 20.

72. The crystalline form of claim 71, characterized as having an XRPD pattern further comprising at least one peak selected from 8.7°, 13.1°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 20 ± 0.4° 20.

73. The crystalline form of any one of claims 63-72, characterized as having an XRPD pattern comprising peaks at 5.7°, 8.4°, 8.7°, 11.7°, 13.1°, 13.9°, 16.6°, 17.5°, 18.3°, 18.7°, 19.2°, 21.2°, and 21.8° 26 ± 0.4° 20.

74. The crystalline form of any one of claims 63-73, characterized as having a XRPD pattern substantially as shown in FIG. 25A.

75. The crystalline form of any one of claims 63-68, characterized as having an XRPD pattern comprising at least three peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 20.

76. The crystalline form of any one of claims 63-68 and 75 characterized as having an XRPD pattern comprising at least five peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 20.

77. The crystalline form of any one of claims 63-68 and 75-76 characterized as having an XRPD pattern comprising at least eight peaks selected from 2.6°, 5.3°, 8.2°, 8.4°, 9.0°, 9.3°, 11.4°, 17.8°, 18.0°, 18.4°, 18.7°, 21.2°, and 23.0° 20 ± 0.4° 26.

78. The crystalline form of any one of claims 75-77, characterized as having a XRPD pattern substantially as shown in FIG. 25D.

79. The crystalline form of any one of claims 63-68 characterized as having an XRPD pattern comprising at least one peak selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 20 ± 0.4° 26.

80. The crystalline form of any one of claims 63-68 and 79 characterized as having an XRPD pattern comprising at least two peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.4° 20.

81. The crystalline form of any one of claims 63-68 and 79-80 characterized as having an XRPD pattern comprising at least four peaks selected from 3.2°, 6.4°, 8.3°, 8.6°, 11.2°, 13.0°, 13.5°, and 17.4° 26 ± 0.4° 20.

82. The crystalline form of any one of claims 66-71 and 90-96, characterized as having a XRPD pattern substantially as shown in FIG. 25E.

83. The crystalline form of any one of claims 63-68 characterized as having an XRPD pattern comprising at least four peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 20 ± 0.4° 20.

84. The crystalline form of any one of claims 63-68 and 83 characterized as having an XRPD pattern comprising at least six peaks selected from 3.2°, 4.7°, 4.9°, 5.3°, 8.4°, 9.6°, 9.9°, 10.9°, 11.0°, 11.3°, 12.6°, 13.8°, 14.9°, 16.0°, 17.8°, 18.3°, 18.5°, 18.9°, 19.2°, 19.4°, 19.6°, 19.9°, 20.6°, 21.8°, and 22.1° 26 ± 0.4° 26.

85. The crystalline form of any one of claims 63-68 and 83-84, characterized as having a XRPD pattern substantially as shown in FIG. 25F.

86. The crystalline form of any one of claims 63-68 characterized as having an XRPD pattern comprising at leastfour peak selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 26 ± 0.4° 26.

87. The crystalline form of any one of claims 63-68 and 86 characterized as having an XRPD pattern comprising at least six peaks selected from 3.3°, 4.5°, 4.8°, 5.1°, 5.3°, 7.2°, 9.7°, 9.9°, 10.1°, 11.2°, 12.4°, 12.8°, 13.2°, 14.6°, 15.2°, 15.3°, 15.5°, 16.1°, 17.2°, 17.6°, 17.8°, 18.3°, 18.6°, 19.0°, 19.3°, 19.6°, 20.0°, 20.6°, 20.9°, 21.2°, 21.7°, 21.9°, 22.4°, 23.3°, 23.7°, 24.4°, and 25.2° 26 ± 0.4° 26.

88. The crystalline form of any one of claims 63-68 and 86-87, characterized as having a XRPD pattern substantially as shown in FIG. 25G.

89. A process for preparing the crystalline form of any one of claims 46-53, wherein the process comprises:(1) dissolving a compound of Formula (XV):(XV), in a first solvent comprising an alcohol and adding a second solvent comprising water to form a crystallization mixture;(2) adjusting the temperature of the crystallization mixture to a first temperature;(3) decreasing the temperature of the crystallization mixture to a second temperature, wherein the second temperature is lower than the first temperature;(4) repeating steps (2)-(3) at least once to provide the crystalline form.

90. The process of claim 89, wherein the alcohol is MeOH or 2-propanol.

91. The process of claim 90, wherein the alcohol is 2-propanol.

92. The process of claims 88-91, wherein the first solvent comprises at least about 95% of the alcohol by volume.

93. The process of any one of claims 88-92, wherein the second solvent is purified water.

94. The process of any one of claims 88-93, wherein the second solvent is an aqueous solution of ammonium acetate.

95. The process of any one of claims 88-94, wherein the compound of Formula (XV) is dissolved in the first solvent at a temperature between about 30 °C and about 40 °C.

96. The process of any one of claims 88-95, wherein prior to step (2), the crystallization mixture is seeded with a crystalline form of the compound of Formula (XV).

97. The process of any one of claims 88-96, wherein the first temperature is between about 10 °C and about 30 °C.

98. The process of any one of claims 88-97, wherein the second temperature is between about 0 °C and about 10 °C.

99. The process of any one of claims 88-98, wherein step (4) comprises repeating steps (2)-(3) at least two times.

100. A crystalline form of a compound of Formula (XIII):(XIII), or a pharmaceutically acceptable salt or solvate thereof.

101. The crystalline form of claim 100, characterized as having an XRPD pattern comprising peaks at 7.6°, 12.6°, 12.9°, 19.8°, and 23.0° 20 ± 0.4° 20.

102. The crystalline form of claim 101, characterized as having an XRPD pattern further comprising at least one peak selected from 10.0°, 13.9°, 14.5°, 15.3°, 16.4°, and 22.4° 20 ± 0.4°26.

103. The crystalline form of any one of claims 100-102, characterized as having an XRPD pattern comprising peaks at 7.6°, 10.0°, 12.6°, 12.9°, 13.9°, 14.5°, 15.3°, 16.4°, 19.8°, 22.4°, and 23.0° 20 ± 0.4° 20.

104. The crystalline form of claim 100, characterized as having a XRPD pattern substantially as shown in FIG. 20.

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