Crystalline solid, aggregate of crystalline solids, method for producing crystalline solid, and kit for preparing crystalline solid

Abstract

The present invention is a crystalline solid comprising a plurality of host molecules, a plurality of co-crystallizable molecules, and a plurality of guest molecules. Each of the co-crystallizable molecules is a molecule capable of affinity interaction with the host molecule, and has a skeleton structure composed of one ring structure or a skeleton structure composed of a plurality of ring structures and a linking structure connecting the ring structures. The plurality of co-crystallizable molecules included in the crystalline solid are each interposed between two or three or more host molecules.

Description

Crystalline solid, aggregate of crystalline solids, method for producing crystalline solids, and kit for producing crystalline solids. 【0001】 This invention relates to crystalline solids, aggregates of crystalline solids, methods for producing crystalline solids, and kits for producing crystalline solids. 【0002】 In recent years, functional materials utilizing host-guest chemistry have attracted attention. For example, Patent Document 1 describes a method for performing crystal structure analysis by regularly arranging molecules of the compound to be analyzed within the pores of a single crystal of a polymer complex and using the resulting guest molecule inclusion complex as a measurement sample (the so-called "molecular structure determination method by crystal sponge method"). 【0003】 Furthermore, Patent Document 2 describes a method for adjusting the guest molecule inclusion ability of a cage-type host molecule by utilizing the interaction between the lid-type molecule and the opening of the cage-type host molecule. Patent Document 2 also describes the molecular structure of the lid-type molecule-cage-type host molecule-guest molecule complex obtained by crystal structure analysis. 【0004】 As shown in Patent Document 2, among cage-type host molecules, those that crystallize easily are useful as molecules for preparing samples for crystal structure analysis. Furthermore, since crystalline solids containing cage-type host molecules are of high purity, they are considered useful as adsorbents, storage molecules for pharmacologically active components, heterogeneous catalysts, etc., even if they do not possess single crystal properties. 【0005】 International Publication No. 2014 / 038220 (US2015 / 0219533) Japanese Patent Publication No. 2022-130321 【0006】As shown in Patent Document 2, the electrical properties of a lid-type molecule-cage-type host molecule complex are usually different from those of the cage-type host molecule. Therefore, it is sometimes possible to promote the precipitation of lid-type molecule-cage-type host molecule complexes by utilizing this change in electrical properties. However, the interaction between the lid-type molecule and the cage-type host molecule is an interaction between one lid-type molecule and one cage-type host molecule, and the lid-type molecule does not interact with multiple cage-type host molecules. Therefore, this interaction does not actively align the orientation of the cage-type host molecules and is considered to contribute little to improving the crystallinity of the precipitate. 【0007】 This invention was made under these circumstances and aims to provide a crystalline solid, an aggregate of crystalline solids, a method for producing a crystalline solid, and a kit for producing a crystalline solid. 【0008】 To solve the above problems, the inventors diligently studied cage-type host molecules. As a result, they discovered that using a molecule capable of affinity interaction with a cage-type host molecule and possessing a specific skeletal structure as a cocrystallizing agent makes it easier to obtain a crystalline solid, thus completing the present invention. 【0009】 Thus, the present invention provides the following crystalline solids [1] to [9], an aggregate of crystalline solids

[10] , a crystalline solid

[11] , an aggregate of crystalline solids

[12] , methods for producing crystalline solids

[13] to

[15] , and a crystalline solid production kit

[16] . 【0010】[1] A crystalline solid comprising a plurality of host molecules, a plurality of cocrystallizable molecules, and a plurality of guest molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them, each of the plurality of cocrystallizable molecules contained in the crystalline solid is interposed between two or three or more host molecules, and all or part of the plurality of host molecules contained in the crystalline solid accommodates the whole molecule or a part of the molecule of a guest molecule in their respective internal spaces. [2] The crystalline solid according to [1], wherein the host molecule is a polynuclear metal complex. [3] The crystalline solid according to [2], wherein the polynuclear metal complex comprises an ion of an element selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt, and a polydentate ligand having a π-conjugated system. [4] The polydentate ligand having a π-conjugated system is of the following formula (1) 【0011】 【0012】A crystalline solid according to [3], wherein the ligand is represented as follows: (A is an m-valent group having aromaticity. X is a divalent organic group or a single bond directly connecting A and Y. Y is a coordinating atom or a monovalent group containing a coordinating atom. m represents an integer from 2 to 6. Multiple Xs may be different from each other, and multiple Ys may be different from each other.) [5] A crystalline solid according to [1], wherein the affinity interaction between the cocrystallizable molecule and the host molecule is one or more interactions selected from the group consisting of hydrophobic interactions, π-π interactions, CH-π interactions, and Coulomb interactions. [6] A crystalline solid according to [1], wherein the skeletal structure of the cocrystallizable molecule is nonplanar. [7] A crystalline solid according to [6], wherein the nonplanar skeletal structure is due to one or more selected from the group consisting of rotational motion around a single bond, steric hindrance, a circular structure, an antiaromatic structure, and a nonplanar linkage structure. [8] The crystalline solid according to [1], wherein it is single-crystallized. [9] The crystalline solid according to [1], wherein it is not single-crystallized.

[10] An aggregate of the crystalline solids according to [1].

[11] A crystalline solid comprising a plurality of host molecules and a plurality of co-crystallizable molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, each co-crystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them, each of the plurality of co-crystallizable molecules contained in the crystalline solid is interposed between two or three or more host molecules, and each of the plurality of host molecules contained in the crystalline solid is in a state in which it can accommodate a guest molecule in its internal space.

[12] An aggregate of the crystalline solids according to

[11] .

[13] A method for producing the crystalline solid described in [1] using the crystalline solid described in

[11] , comprising the step (step a-I) of accommodating the guest molecule in the internal space of all or some of the host molecules contained in the crystalline solid by coexisting the crystalline solid described in

[11] and the guest molecule in the same system in the presence or absence of a solvent.

[14] A method for producing the crystalline solid described in [1] using a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and linking structures connecting them, the method for producing the crystalline solid described in [1], comprising: a step of preparing a solution containing the host molecule, a guest molecule, and a cocrystallizable molecule (step b-I); and a step of precipitating a crystalline solid containing the host molecule containing the guest molecule and the cocrystallizable molecule from the solution obtained in step b-I (step b-II).

[15] A method for producing a crystalline solid using a crystal holder, wherein the crystal holder has a crystal fixing portion and a shape that can be fixed directly or via other parts to a goniometer of a crystal structure analysis apparatus, and step b-II is performed with the solution obtained in step b-I in contact with the crystal fixing portion of the crystal holder, as described in

[14] .

[16] A crystalline solid production kit having a combination of a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more wall portions, and an internal space surrounded by the wall portions, and the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures connecting them, as described in the crystalline solid production kit. 【0013】The present invention provides a crystalline solid, an aggregate of crystalline solids, a method for producing a crystalline solid, and a kit for producing a crystalline solid. In the following, a crystalline solid containing multiple host molecules, multiple co-crystallizable molecules, and multiple guest molecules is described as crystalline solid 1, and a crystalline solid containing multiple host molecules and multiple co-crystallizable molecules but not guest molecules is described as crystalline solid 2. 【0014】 This figure shows the host molecule, co-crystallizable molecule, and guest molecule in the crystalline solid obtained in Example 1. This figure shows the host molecule, co-crystallizable molecule, and guest molecule in the crystalline solid obtained in Example 5. This figure shows the host molecule, co-crystallizable molecule, and guest molecule in the crystalline solid obtained in Example 6. 【0015】 The present invention will be described in detail below, divided into the following sections: 1) Crystalline solid 1 and its aggregate, 2) Crystalline solid 2 and its aggregate, 3) Method for producing crystalline solid 1, and 4) Crystalline solid production kit. 【0016】 1) Crystalline Solid 1 and its Assembly The crystalline solid 1 of the present invention comprises a plurality of host molecules, a plurality of cocrystallizable molecules, and a plurality of guest molecules. Each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls. Each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them. Each of the plurality of cocrystallizable molecules contained in the crystalline solid 1 is interposed between two or three or more host molecules. All or part of the plurality of host molecules contained in the crystalline solid 1 accommodate the whole molecule or a part of the molecule of a guest molecule in their respective internal spaces. 【0017】In this specification, "molecule" includes not only electrically neutral substances composed of two or more atoms, but also charged substances (ions) composed of two or more atoms. "Host molecule" means a molecule having an opening, a wall, and an internal space, and having the ability to accommodate a guest molecule in the internal space. "Opening" means the part that functions as an entrance to the internal space. "Wall" means the part that separates the inside and outside of the host molecule. "Internal space" means the space enclosed by the wall. There are no restrictions on the shape of the internal space as long as it can accommodate a guest molecule; for example, it may be elongated, like a "pore." "Guest molecule" means a molecule that is accommodated in the internal space of a host molecule. In this specification, the term "guest molecule" is used not only for molecules that are accommodated in the internal space of a host molecule, but also for molecules that are not yet accommodated. "Accommodating a guest molecule in the internal space" includes not only the state in which the entire guest molecule is completely contained within the internal space, but also the state in which a part of the guest molecule is contained within the internal space and the remaining part of the guest molecule protrudes from the opening. A "cocrystallizing molecule" refers to a molecule that, when added to a solution containing a dissolved host molecule, functions as a cocrystallizing agent (coformer) and causes the formation of a cocrystal. 【0018】 [Host Molecule] A host molecule contained in the crystalline solid 1 is a molecule having one or more openings, one or more walls, and an internal space surrounded by the walls. 【0019】 An opening is a portion that functions as an entry point for a guest molecule into the internal space. The shape and size of the opening are not particularly limited, as long as the guest molecule can pass through. When the largest circle inscribed in the opening is considered, its diameter is, for example, 0.1 to 5 nm, preferably 0.3 to 3 nm. The number of openings contained in the host molecule is usually 1 to 10, preferably 1 to 5. 【0020】 The wall portion functions as a barrier separating the inside and outside of the host molecule. As will be discussed later, the wall portion may interact favorably with cocrystallizable molecules. 【0021】The internal space is the space inside the host molecule and is the part that accommodates the guest molecule. As long as the guest molecule can be accommodated, the size of the internal space is not particularly limited. The internal space may be partitioned by molecular chains or the like and have a plurality of small spaces. 【0022】 The overall charge of the host molecule contained in the crystalline solid 1 is positive, negative, or uncharged. By adjusting the combination with the cocrystallizable molecule, the crystalline solid 1 can be efficiently precipitated. Therefore, the overall charge of the host molecule is preferably positive or negative. When using a polynuclear metal complex described later as the host molecule, since the polynuclear metal complex contains many metal ions, usually, the host molecule has a positive charge as a whole. 【0023】 The size of the host molecule is not particularly limited. When a virtual rectangular parallelepiped that can accommodate the host molecule is considered, the length of the longest side of the rectangular parallelepiped is, for example, 0.3 to 15 nm, preferably 1 to 10 nm, and the length of the shortest side is, for example, 0.3 to 15 nm, preferably 0.5 to 10 nm. 【0024】 As the host molecule, a polynuclear metal complex is preferable because molecular design is relatively easy. A polynuclear metal complex is a metal complex containing two or more metal ions and ligands. Examples of the polynuclear metal complex used as the host molecule include a three-dimensional metal complex containing two or more metal ions and a ligand having two or more coordination sites and having a space inside. In this polynuclear metal complex, usually, the wall portion of the host molecule is constructed by the ligand and the metal ion. 【0025】 The metal ion is not particularly limited as long as it can form a polynuclear metal complex. As the metal ion, ions of elements selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt are preferable, and ions of elements in Group 8, Group 9, or Group 10 of the periodic table are more preferable. The valence of the metal ion is not particularly limited and is usually 1 to 4, preferably 1 to 3, and more preferably 2. 【0026】As the ligand, there are ligands that constitute the wall portion of the host molecule (hereinafter sometimes referred to as "ligand (α)"), and ligands that play other roles (roles such as adjusting the charge of the polynuclear metal complex, occupying the vacant coordination sites of metal ions, and suppressing the polymerization of the polynuclear metal complex) (hereinafter sometimes referred to as "ligand (β)"). 【0027】 As the ligand (α), a polydentate ligand having a π-conjugated system is preferable. When the ligand (α) is a ligand having a π-conjugated system, an affinity interaction with the cocrystallizable molecule may easily occur. In addition, when the ligand (α) is a polydentate ligand, a host molecule having an internal space suitable for accommodating the guest molecule is easily obtained. As the polydentate ligand having a π-conjugated system, a polydentate ligand containing an aromatic group as a central skeleton is preferable. Since the polydentate ligand containing an aromatic group as a central skeleton is relatively rigid and excellent in planarity, the structure of the host molecule is easily maintained. As the ligand (α), for example, those represented by the following formula (1) can be mentioned. 【0028】 【0029】 In formula (1), A is an m-valent group having aromaticity. X is a divalent organic group or a single bond directly connecting between A and Y. Y is a coordinating atom or a monovalent group containing a coordinating atom. m represents an integer of 2 to 6. A plurality of Xs may be different from each other, and a plurality of Ys may be different from each other. 【0030】 The number of atoms (excluding hydrogen atoms) of the group represented by A is usually 6 to 100, preferably 6 to 60, more preferably 6 to 30. Examples of the group represented by A include an aromatic group of a 6-membered ring, a group formed by connecting a plurality of aromatic groups of 6-membered rings with a single bond, a group having a porphyrin skeleton, and the like. 【0031】 Examples of the aromatic group of the 6-membered ring include groups having an aromatic ring such as a benzene ring, a triazine ring, a pyridine ring, and a pyrazine ring. The aromatic group of the 6-membered ring may have a substituent other than -(-X-Y). Examples of the substituent include an alkyl group having 1 to 10 carbon atoms; a halogen atom such as a fluorine atom, a bromine atom, and a chlorine atom; and the like. 【0032】 The following are examples of bases represented by A, but are not limited to these. Note that "*" represents a bond (a bond position with X). 【0033】 【0034】 【0035】 In the above formula, M represents a metal ion. Examples of metal ions include those similar to those exemplified as metal ions constituting polynuclear metal complexes. Among these, zinc ions are preferred. 【0036】 The number of atoms in the group represented by X (excluding hydrogen atoms) is usually 1 to 30, preferably 2 to 20, and more preferably 2 to 10. Examples of the group represented by X include the divalent group represented by A, a methylene group, an ethylene group, 1,2-ethendiyl, 1,2-ethingiyl (acetylene group), a p-phenylene group, an m-phenylene group, and other hydrocarbon groups, an amide group (-C(=O)-NH-), an ester group (-C(=O)-O-), and an oxymethylene group (-O-CH ２ -), oxyethylene group (-O-CH ２ CH ２ Examples include, but are not limited to, the group represented by X. Furthermore, the group represented by X may be a group formed by the bonding of two or more of these groups. Examples of such groups include, but are not limited to, the following: 【0037】 【0038】 Examples of coordinating atoms represented by Y include oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, etc. The number of atoms in a monovalent group represented by Y (excluding hydrogen atoms) is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10. Examples of monovalent groups represented by Y include pyridyl groups, amino groups, hydroxyl groups, deprotonated amide groups, carboxylate groups, sulfonate groups, phosphonate groups, dithiocarboxylate groups, cyano groups, and groups containing these groups as substituents. Examples of monovalent groups represented by Y include the following: 【0039】 【0040】 Examples of the ligand (α) include, but are not limited to, the following. 【0041】 【0042】 【0043】 【0044】 As the ligand (α), ligands other than those represented by the formula (1) can also be used. Examples of such ligands include, for example, the following. 【0045】 【0046】 The ligand (β) is preferably a relatively low molecular weight ligand. The low molecular weight ligand is less likely to have an adverse effect such as steric hindrance on the coordination of the ligand (α). Examples of the ligand (β) include monodentate ligands or chelate ligands. 【0047】 Examples of the monodentate ligand used as the ligand (β) include divalent anions such as oxide ions (O ２－ ); monovalent anions such as hydroxide ions (OH － ), chloride ions (Cl － ), bromide ions (Br － ), iodide ions (I － ), thiocyanate ions (SCN － ); electrically neutral coordinating compounds such as water, ammonia, monoalkylamines, dialkylamines, trialkylamines; etc. 【0048】 Examples of the chelate ligand used as the ligand (β) include bidentate chelate ligands such as ethylenediamine, N,N'-dimethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,2-cyclohexanediamine, N,N,N',N'-tetramethyl-1,2-cyclohexanediamine, 2,2'-bipyridyl, etc., but are not limited thereto. 【0049】By appropriately selecting metal ions, ligand (α), and ligand (β), and utilizing conventionally known methods, multinuclear metal complexes that can be used as host molecules can be synthesized. Furthermore, known multinuclear metal complexes with inclusion ability can be used as host molecules. An example of such a multinuclear metal complex is shown below, along with the ligand (α) that constitutes it. When expressing the ratio of metal ions and ligand (α) constituting the multinuclear metal complex, the metal ion is represented as "M", ligand (α) as "L", and the second ligand (α) as "X" if necessary. 【0050】 【0051】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ４ ] 【0052】 【0053】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ４ ] 【0054】 【0055】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ３ In the ligand represented by L, M represents a metal ion such as a Zn ion. 【0056】 【0057】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ２ X ３ ] 【0058】 【0059】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L １ ] 【0060】 【0061】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M １２ L ２ ] 【0062】 【0063】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M １２ L ４ ] 【0064】 【0065】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratios of the polynuclear metal complex on the left are [M １０ L ４ ] and the main component ratio of the polynuclear metal complex on the right is [M ８ L ４ ] 【0066】 【0067】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratios of the polynuclear metal complex on the left are [M ８ L ４ ] and the main component ratio of the polynuclear metal complex on the right is [M ６ L ４ ] 【0068】 【0069】In the above formula, Pt represents a platinum ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ４ L ４ ] 【0070】 【0071】 In the schematic diagram above, the sphere represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ２ ] 【0072】 【0073】 In the schematic diagram above, the sphere represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M １２ L ４ ] 【0074】 Details regarding the synthesis methods of these multinuclear metal complexes are described in International Publication No. 2018 / 159692. 【0075】 [Cocrystallizable Molecules] Cocrystallizable molecules contained in crystalline solid 1 are molecules capable of affinity interaction with host molecules. Because cocrystallizable molecules are capable of affinity interaction with host molecules, they readily interpose between host molecules when functioning as cocrystallizing agents. 【0076】 Affinity interactions between cocrystallizable molecules and host molecules include hydrophobic interactions, π-π interactions, CH-π interactions, and Coulomb interactions. Multiple affinity interactions may occur between cocrystallizable molecules and host molecules. Among these, π-π interactions and Coulomb interactions are preferred as affinity interactions between cocrystallizable molecules and host molecules because they are larger interactions. 【0077】Cocrystallizable molecules are preferably those possessing π-conjugated systems or anionic groups. The presence of π-conjugated systems or anionic groups in cocrystallizable molecules facilitates affinity interactions between the cocrystallizable molecule and the host molecule. The π-conjugated system of a cocrystallizable molecule tends to interact with ligands and other components of the host molecule, while the anionic groups tend to interact with metal ions constituting the host molecule. Furthermore, if the host molecule is a polynuclear metal complex, the host molecule as a whole tends to carry a positive charge. In this case, a cocrystallizable molecule possessing anionic groups and carrying a negative charge as a whole can function as a counterion. 【0078】 Examples of anionic groups include carboxylate ion groups, sulfonate ion groups, and phosphate ion groups, with carboxylate ion groups and sulfonate ion groups being preferred. 【0079】 Cocrystallizable molecules have a skeletal structure composed of either a single ring structure or multiple ring structures connected by linking structures. The skeletal structure refers to the central structure of a cocrystallizable molecule, specifically the part where intramolecular motion is restricted by the ring structure. Because cocrystallizable molecules possess this skeletal structure, their molecular structure does not change significantly. Therefore, by selecting a cocrystallizable molecule suitable for the shape of the host molecule, it is possible to fully express affinity interactions between the cocrystallizable molecule and the host molecule. 【0080】 The ring structures that make up the skeletal structure include aromatic ring structures such as monocyclic aromatic rings and fused aromatic rings, as well as alicyclic structures. The linking structures that make up the skeletal structure include single bonds that connect two ring structures, hydrocarbon groups such as ethene-1,1,2,2-tetrayl groups, and quaternary carbon atoms. 【0081】 The skeletal structure may be planar or nonplanar. A planar skeletal structure is one in which all atoms constituting the skeletal structure are located on the same plane, while a nonplanar skeletal structure is any structure other than a planar skeletal structure. 【0082】Examples of planar skeletal structures include pyrene skeletons, naphthalene skeletons, and benzene skeletons. Cocrystallizable molecules with planar skeletal structures tend to interpose between the walls of two host molecules, aligning the orientation of the host molecules. 【0083】 Examples of cocrystallizable molecules having a planar skeletal structure include those represented by the following formula. 【0084】 【0085】 In the formula, each R independently represents either an anionic group or a hydrogen atom, and at least one R in the molecule is an anionic group. 【0086】 Examples of non-planar skeletal structures include those represented by the following formula. 【0087】 【0088】 The causes of these non-planar skeletal structures include rotational motion around single bonds, steric hindrance, circular structures, anti-aromatic structures, non-planar linkage structures, and combinations thereof. Cocrystallizable molecules with non-planar skeletal structures have difficulty interacting strongly with the walls of host molecules. For this reason, cocrystallizable molecules with non-planar skeletal structures usually have multiple anionic groups, and these anionic groups interact with transition metal ions. 【0089】 Examples of cocrystallizable molecules having a non-planar skeletal structure include those represented by the following formula. 【0090】 【0091】 In the formula, each R independently represents either an anionic group or a hydrogen atom, and at least one R in the molecule is an anionic group. 【0092】 As shown in the molecular structure above, some cocrystallizable molecules with a non-planar skeletal structure are capable of intramolecular motion, such as rotational motion around the carbon-carbon single bond. However, even when such intramolecular motion occurs, the distance between R and R remains constant in the stable and metastable states. For this reason, stable Coulomb interactions are likely to occur between anionic groups and transition metal ions. 【0093】 [Guest Molecules] The guest molecules contained in the crystalline solid 1 are molecules that are housed in the internal space of the host molecule. The form of the guest molecules is not particularly limited and may be in a solid state, liquid state, or gas state at room temperature (20°C). The molecular weight of the guest molecules is usually 2,000 or less, preferably 800 or less. There is no particular lower limit for the molecular weight of the guest molecules, but it is usually 50 or more. 【0094】 As will be described later, in crystalline solid 1, guest molecules can occupy not only the internal space of the host molecules but also the space between host molecules. For this reason, in crystalline solid 1, molecules that are not suitable as guest molecules in conventional host-guest chemistry (relatively large molecules, polar molecules, amphiphilic molecules, etc.) can also become guest molecules. 【0095】 [Crystalline Solid 1] In crystalline solid 1, multiple co-crystallizable molecules are interposed between two or more host molecules. In this way, the presence of co-crystallizable molecules between multiple host molecules and the affinity interaction between the co-crystallizable molecules and multiple host molecules causes the orientation of the host molecules to align, thereby increasing the crystallinity of crystalline solid 1. 【0096】 By changing the type of cocrystallizable molecule used, the affinity interaction between the cocrystallizable molecule and the host molecule can be altered, potentially allowing for adjustment of the size and properties of the space between the host molecules. This can be used to prepare a crystalline solid 1 having both an internal space (hydrophobic space) within the host molecule and a hydrophilic space between the host molecules. 【0097】In crystalline solid 1, it is preferable that the host molecule and the co-crystallizable molecule have different charges. Specifically, this includes cases where the overall charge of the host molecule is positive and the overall charge of the co-crystallizable molecule is negative, or where the overall charge of the host molecule is negative and the overall charge of the co-crystallizable molecule is positive. When the host molecule and the co-crystallizable molecule have different charges, the co-crystallizable molecule functions as a counterion of the host molecule, allowing for efficient deposition of crystalline solid 1 from solution. Furthermore, crystalline solid 1 in which the host molecule and the co-crystallizable molecule have different charges exhibits excellent stability. Moreover, crystalline solid 1 containing a host molecule and a co-crystallizable molecule with different charges is often precipitated from an aqueous solution, and in this case, the spaces between the host molecules in crystalline solid 1 tend to be hydrophilic. 【0098】 Crystalline solid 1 may contain one type of cocrystallizable molecule, or it may contain two or more types. 【0099】 In a crystalline solid 1, all or some of the multiple host molecules contain a guest molecule, either entirely or partially, within their respective internal spaces. That is, in a crystalline solid 1 where there is little or no space between host molecules, the entire guest molecule is usually contained only within the internal space of the host molecule. However, in a crystalline solid 1 designed to allow guest molecules to occupy not only the internal space of the host molecules but also the spaces between them, the guest molecule may be contained within both the internal space of the host molecules and the spaces between them. Therefore, in a crystalline solid 1 designed to allow guest molecules to occupy the spaces between host molecules as well, even relatively large guest molecules, polar molecules, amphiphilic molecules, etc., can sometimes be stably contained. 【0100】Crystalline solid 1 may have molecules other than the cocrystallizable molecules used in the present invention between the host molecules. Examples of such molecules include the lid-like molecules described in Japanese Patent Application Publication No. 2022-130321, and molecules having properties or molecular structures not included in the cocrystallizable molecules used in the present invention. When the combination of host molecules and cocrystallizable molecules is not optimized, the presence of these molecules between the host molecules may stabilize crystalline solid 1 and increase its crystallinity. 【0101】 The crystalline solid 1 may or may not be single-crystal. A crystalline solid 1 having single crystallinity is preferably used as a sample for crystal structure analysis. That is, when the crystalline solid 1 has single crystallinity, multiple host molecules assemble regularly in three dimensions, and all or part of these host molecules regularly accommodate the entire or a part of a guest molecule in their respective internal spaces in three dimensions. Therefore, by performing crystal structure analysis using a crystalline solid 1 having single crystallinity, the molecular structure of the guest molecule can be revealed. Note that the expressions "multiple host molecules assemble regularly in three dimensions" and "multiple guest molecules regularly accommodate in three dimensions" refer to a state in which the molecular structure of the host molecule or the molecular structure of the guest molecule can be determined by crystal structure analysis, respectively. 【0102】 The size of the crystalline solid 1 used as a sample for crystal structure analysis is not particularly limited. A crystalline solid 1 suitable for the crystal structure analysis apparatus used should be selected as the sample for crystal structure analysis. For example, when performing crystal structure analysis using a commercially available X-ray crystal structure analyzer, if we consider the smallest rectangular parallelepiped that can accommodate the crystalline solid 1, the length of its long side is usually 10 to 500 μm, preferably 50 to 500 μm, and the length of its short side is usually 10 to 500 μm, preferably 10 to 200 μm. 【0103】When determining the molecular structure based on the collected diffraction intensity data after irradiating multiple crystal structure analysis samples with synchrotron X-rays, if we consider the smallest rectangular parallelepiped capable of containing the crystalline solid 1, the length of its long side is usually 0.1 to 100 μm, preferably 1 to 100 μm, and the length of its short side is usually 0.1 to 100 μm, preferably 1 to 10 μm. 【0104】 When performing crystal structure analysis by microelectron diffraction, when the smallest rectangular parallelepiped capable of containing the crystalline solid 1 is considered, the length of its long side is usually 0.1 to 1000 nm, preferably 1 to 1000 nm, and the length of its short side is usually 0.1 to 100 nm, preferably 0.1 to 10 nm. 【0105】 Examples of crystalline solids 1 that do not possess single-crystal properties include adsorbents containing adsorbed target substances, storage materials containing dye molecules or pharmacologically active components, heterogeneous catalysts, and sustained-release composites. Crystalline solids 1 have the characteristic that the arrangement of host molecules can be controlled by adjusting the combination of host molecules and co-crystallizable molecules. Furthermore, crystalline solids 1 are usually of high purity. Due to these characteristics, crystalline solids 1 are suitably used as the above-mentioned functional materials. 【0106】 The size of the crystalline solid 1 that does not possess single crystallization is not particularly limited, and a crystalline solid 1 of an appropriate size should be selected depending on the application. Furthermore, when the crystalline solid 1 is used as the functional material described above, a single crystal is usually not used, but rather it is used in the form of an aggregate of crystalline solids 1, as described later. 【0107】[Aggregate of Crystalline Solid 1] The aggregate of crystalline solid 1 of the present invention is an aggregate composed of multiple crystalline solids 1. When performing crystal structure analysis using a commercially available X-ray crystallography system, if a high-quality single crystal is obtained, the objective is usually achieved with just that one crystal. On the other hand, there are cases where multiple crystals are required to achieve a predetermined objective. The aggregate of crystalline solid 1 of the present invention is used in such cases. Thus, in the present invention, "aggregate" means a group for achieving a predetermined objective. Therefore, the aggregate of crystalline solid 1 is not limited to twins or multiple crystals bundled together, but may also be a microcrystalline powder, etc. 【0108】 An aggregate of crystalline solids 1 having single crystallization properties is suitably used, for example, when determining the molecular structure based on the collected diffraction intensity data after irradiating multiple crystal structure analysis samples with synchrotron X-rays. Furthermore, an aggregate of crystalline solids 1 that does not have single crystallization properties is suitably used, for example, when used as the functional material described above. 【0109】 2) Crystalline Solid 2 and its Aggregate [Crystalline Solid 2] The crystalline solid 2 of the present invention comprises a plurality of host molecules and a plurality of cocrystallizable molecules. Each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls. Each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them. The plurality of cocrystallizable molecules contained in the crystalline solid 2 are each interposed between two or three or more host molecules. The plurality of host molecules contained in the crystalline solid 2 are in a state in which they can accommodate a guest molecule in their respective internal spaces. 【0110】 Crystalline solid 2 is similar to crystalline solid 1, except that the guest molecule is not housed in the internal space of the host molecule. 【0111】 The method for producing the crystalline solid 2 is not particularly limited. For example, the crystalline solid 2 can be obtained by preparing a solution containing a host molecule and a cocrystallizable molecule, and allowing it to stand to precipitate as a crystalline solid. 【0112】 The concentration of the host molecule in the solution containing the host molecule and the cocrystallizable molecule is usually 0.1 to 50 mM, preferably 5 to 20 mM. The amount of the cocrystallizable molecule in the solution containing the host molecule and the cocrystallizable molecule is usually 0.1 to 10 equivalents, preferably 0.1 to 4 equivalents, relative to the host molecule. The temperature of the solution when precipitating the crystalline solid 2 is usually 0 to 80°C, preferably 4 to 50°C. The standing time when precipitating the crystalline solid 2 is usually 1 to 240 hours, preferably 1 to 24 hours. 【0113】 [Aggregate of Crystalline Solid 2] The aggregate of crystalline solid 2 of the present invention is an aggregate composed of a plurality of crystalline solids 2. The aggregate of crystalline solid 2 is the same as the aggregate of crystalline solid 1, except that its constituent component is crystalline solid 2. The aggregate of crystalline solid 2 is usually used as a precursor of the aggregate of crystalline solid 1. Therefore, for example, by incorporating guest molecules into the internal space of each crystalline solid 2 constituting the aggregate of single-crystal crystalline solid 2, a sample for synchrotron X-ray crystal structure analysis can be obtained. 【0114】 3) Method for producing the crystalline solid 1 The method for producing the crystalline solid 1 of the present invention is not particularly limited. For example, the crystalline solid 1 can be produced by the following method (A) or method (B). 【0115】 [Manufacturing Method (A)] Manufacturing method (A) includes a step (step a-I) in which a crystalline solid 2 and a guest molecule are brought together in the same system, either in the presence or absence of a solvent, thereby accommodating the guest molecule in the internal space of all or some of the host molecules contained in the crystalline solid 2. 【0116】 "To have crystalline solid 2 and a guest molecule coexist in the same system" means to place these components in a state where they can come into contact with each other. Therefore, the "same system" does not necessarily have to be a single-phase system as a whole. 【0117】One example of a state in which crystalline solid 2 and guest molecules coexist in the same system in the presence of a solvent is a state in which crystalline solid 2 is immersed in a solution or suspension formed when at least a portion of the guest molecules dissolve in the solvent. In this case, it is important that the immersed crystalline solid 2 does not dissolve in the solution or suspension. For example, crystalline solid 1 can be produced by bringing crystalline solid 2 into contact with guest molecules using a solvent in which crystalline solid 2 does not dissolve, or by utilizing the mother liquor produced when crystalline solid 2 was manufactured. 【0118】 Examples of states in which crystalline solid 2 and guest molecules coexist in the same system without a solvent include placing crystalline solid 2 in a container containing gaseous guest molecules, or immersing crystalline solid 2 in liquid guest molecules. 【0119】 After the guest molecules come into contact with the crystalline solid 2, they are accommodated within the internal space of the host molecules that make up the crystalline solid 2. If the crystalline solid 2 is single-crystal and the guest molecules are regularly accommodated, a single-crystal crystalline solid 1 is obtained. 【0120】 The amount of guest molecules to be present with the crystalline solid 2 is usually 0.1 mol or more, preferably 0.5 mol or more, per 1 mol of host molecules. 【0121】 The conditions for accommodating the guest molecule in the internal space of the host molecule constituting the crystalline solid 2 are not particularly limited. The temperature for accommodating the guest molecule in the internal space of the host molecule is usually 0 to 100°C, preferably 20 to 100°C. The time for accommodating the guest molecule in the internal space of the host molecule is usually 30 seconds to 72 hours, preferably 0.5 to 24 hours. 【0122】The solvents used in manufacturing method (A) include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, and nitrobenzene; aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cycloheptane; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide (DMSO); amides such as N,N-dimethylformamide and n-methylpyrrolidone; ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; esters such as methyl acetate, ethyl acetate, ethyl lactate, and ethyl propionate; and water. These solvents can be used individually or in combination of two or more. 【0123】 [Manufacturing Method (B)] Manufacturing method (B) comprises the steps of: preparing a solution containing a host molecule, a guest molecule, and a cocrystallizable molecule (step b-I); and precipitating a crystalline solid 1 containing a host molecule containing a guest molecule and a cocrystallizable molecule from the solution obtained in step b-I (step b-II). 【0124】 The host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls. The cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and linking structures connecting them. The details of these molecules are the same as those of the host molecule and cocrystallizable molecule that constitute the crystalline solid 1. 【0125】Step b-I is the step of preparing a solution containing a host molecule, a guest molecule, and a cocrystallizable molecule. The order in which the components are mixed and the state of each component (solution state, pure substance state, etc.) are not particularly limited, as long as the desired solution is prepared. For example, the solutions of each component may be mixed simultaneously, or the guest molecule may be added in solution state or pure substance state to a solution in which the host molecule and cocrystallizable molecule are dissolved, or the cocrystallizable molecule may be added in solution state or pure substance state to a solution in which the host molecule and guest molecule are dissolved. 【0126】 The concentration of the host molecule in the solution obtained in step b-I is usually 0.1 to 50 mM, preferably 1 to 20 mM. The amount of cocrystallizable molecules in the solution obtained in step b-I is usually 0.1 to 10 equivalents, preferably 0.1 to 4 equivalents, relative to the host molecule. The amount of guest molecules in the solution obtained in step b-I is usually 0.1 equivalents or more, preferably 1 equivalent or more, relative to the host molecule. 【0127】 Step b-II is a step in which a crystalline solid 1 containing a host molecule containing a guest molecule and a cocrystallizable molecule is precipitated from the solution obtained in step b-I. The temperature of the solution when precipitation of the crystalline solid 1 is usually 0 to 80°C, preferably 4 to 50°C. The standing time when precipitation of the crystalline solid 1 is usually 1 to 240 hours, preferably 1 to 24 hours. 【0128】 The solvent used in manufacturing method (B) is the same as the solvent used in manufacturing method (A). 【0129】 When manufacturing a crystalline solid 1 to be used as a sample for crystal structure analysis, it is preferable to use the crystal holder described below to carry out manufacturing method (B) in order to efficiently install the sample for crystal structure analysis into the crystal structure analysis apparatus. The crystal holder is an instrument having a crystal fixing part and a shape that can be fixed directly or via other parts to the goniometer of the crystal structure analysis apparatus. 【0130】The crystal holder has a crystal fixing portion. The crystal fixing portion is the place where the crystalline solid 1 is fixed. The shape of the crystal fixing portion is not particularly limited. Examples include capillary shape, rod shape, wire shape, mesh shape, multi-hole plate shape, dish shape, plate shape, thin film shape, etc. 【0131】 The crystal holder has a shape that allows it to be fixed directly or via other components to the goniometer of a crystal structure analysis apparatus. Because the crystal holder has this shape, the conventional procedure of fixing the crystal structure analysis sample to the tip of a glass rod or inside a capillary, which was performed before crystal structure analysis, can be omitted. 【0132】 Examples of shapes that can be fixed to the goniometer of a crystal structure analysis apparatus include capillary, rod, and plate shapes. However, it is not limited to these. When the shape of the crystal holder that can be fixed to the goniometer of a crystal structure analysis apparatus is capillary or rod-shaped, the crystal holder can be efficiently fixed to the goniometer of the crystal structure analysis apparatus using the goniometer head of a conventional crystal structure analysis apparatus. 【0133】 When performing manufacturing method (B) using a crystal holder, by performing step b-II while the solution obtained in step b-I is in contact with the crystal fixing part of the crystal holder, a single crystal (crystalline solid 1) can be precipitated on the surface of the crystal fixing part of the crystal holder. For example, if the crystal holder is a capillary, a solution containing host molecules, guest molecules, and cocrystallizable molecules can be filled into the capillary using capillary action and left to stand, thereby precipitating a single crystal (crystalline solid 1) on the inner wall of the capillary. By using a capillary as the crystal holder, crystalline solid 1 can be produced with a small amount of solution. Therefore, this method is preferably used when the amount of guest molecules is small. 【0134】 4) Crystalline Solid Preparation Kit The sample preparation kit for crystal structure analysis of the present invention comprises a combination of a host molecule and a cocrystallizable molecule. 【0135】The host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls. The cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and linking structures connecting them. The details of these molecules are the same as those of the host molecule and cocrystallizable molecule that constitute the crystalline solid 1. 【0136】 The host molecule and co-crystallizable molecule constituting the crystalline solid preparation kit of the present invention may be in a pure substance state or in a solution state. The crystalline solid preparation kit of the present invention may contain two or more host molecules and / or two or more co-crystallizable molecules. 【0137】 By using the crystalline solid fabrication kit of the present invention, crystalline solid 1 and crystalline solid 2 can be efficiently manufactured. 【0138】 The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples. 【0139】 [Synthesis Example 1] [{(N,N,N',N'-tetramethylethylenediamine)palladium} ６ (2,4,6-Tris(4-pyridyl)-1,3,5-triazine) ４ Nitrate synthesis Nitrates of the octahedral metal complexes shown below (hereinafter sometimes referred to as "host molecule (i)") were synthesized according to the method described in J. Am. Chem. Soc., 2004, 126, 9172-9173. 【0140】 【0141】 [Synthesis Example 2] In Synthesis Example 1, (N,N,N',N'-tetramethyl-1,2-cyclohexanediamine)palladium nitrate was used instead of (N,N,N',N'-tetramethylethylenediamine)palladium nitrate to synthesize a nitrate of a chiral octahedral metal complex (hereinafter sometimes referred to as "host molecule (ii)"). 【0142】[Synthesis Example 3] Synthesis of 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrakis(sodium benzenesulfonate) 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrakis(sodium benzenesulfonate) (hereinafter sometimes referred to as "cocrystallizable molecule (iii)") was synthesized according to the method described in New J. Chem., 2017, 41, 4747-4749. 【0143】 【0144】 [Synthesis Example 4] Synthesis of 1,3,4,6-benzenetetramethanesulfonate sodium salt 1,3,4,6-benzenetetramethanesulfonate sodium salt (hereinafter sometimes referred to as "cocrystallizable molecule (iv)") was synthesized according to the method described in ACS Catal. 2018, 8, 2519-6996. 【0145】 【0146】 [Single-crystal X-ray crystal structure analysis] Single-crystal X-ray crystal structure analysis was performed using a Rigaku Synergy-S diffuser [Cu-Kα rays (wavelength 1.5418 Å)]. 【0147】 [Crystal Deposition Method] An aqueous solution of the host molecule, an aqueous solution of the cocrystallizable molecule, and the guest molecule were mixed. Using capillary action, the resulting mixture was filled into a glass capillary approximately 0.3 mm in diameter and 5 cm in length, and this was transferred to a sealed container at 60°C. The temperature of the sealed container was lowered to 20°C, and the container was left to stand for 12 hours to precipitate crystals inside the glass capillary. 【0148】[Example 1] In the crystal precipitation method described above, an aqueous solution of nitrate of host molecule (i) (concentration 20 mM, 50 μL) was used as the aqueous solution of the host molecule, an aqueous solution of cocrystallizable molecule (iii) (concentration 20 mM, 10 μL) was used as the aqueous solution of the cocrystallizable molecule, and (±)-Evodiamine (20 μg) was used as the guest molecule to precipitate crystals in a glass capillary. The glass capillary was removed from the sealed container and attached to a goniometer head for X-ray crystal structure analysis. Figure 1 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 1, (±)-Evodiamine is contained in the internal space of host molecule (i). Cocrystallizable molecule (iii) is present between the two host molecules (i), and its sulfonate ion group is in close proximity to the palladium ion of host molecule (i). 【0149】 【0150】 [Example 2] Except for using Colchicinine (20 μg) instead of (±)-Evodiamine (20 μg) as in Example 1, crystals were precipitated and X-ray crystal structure analysis was performed using the same method as in Example 1. As a result, it was found that, similar to Example 1, Colchicinine was contained within the internal space of host molecule (i), and furthermore, a cocrystallizable molecule (iii) was present between the two host molecules (i). 【0151】 【0152】 [Example 3] Except for using Strychnine (20 μg) instead of (±)-Evodiamine (20 μg) as in Example 1, crystals were precipitated and X-ray crystal structure analysis was performed using the same method as in Example 1. As a result, it was found that, similar to Example 1, Strychnine was contained in the internal space of host molecule (i), and furthermore, a cocrystallizable molecule (iii) was present between the two host molecules (i). 【0153】 【0154】[Example 4] Except for using rac-cis-decalin (1 μL) instead of (±)-Evodiamine (20 μg) in Example 1, and adding Perylene (100 μg) to the crystallization solution, crystals were precipitated in the same manner as in Example 1 and X-ray crystal structure analysis was performed. As a result, it was found that rac-cis-decalin and perylene were housed in the internal space of host molecule (i). Furthermore, a cocrystallizable molecule (iii) was present between the two host molecules (i). 【0155】 【0156】 [Example 5] In the crystal precipitation method described above, an aqueous solution of nitrate of host molecule (ii) (concentration 5 mM, 100 μL) was used as the aqueous solution of the host molecule, an aqueous solution of cocrystallizable molecule (iii) (concentration 20 mM, 5 μL) was used as the aqueous solution of the cocrystallizable molecule, Lovastatin (20 μg) was used as the guest molecule, and a mixed solution containing an aqueous solution of 1,3,5-benzenetrimethanesulfonate sodium salt (concentration 100 mM, 1 μL) was prepared, and crystals were precipitated in a glass capillary. The glass capillary was removed from the sealed container and attached to a goniometer head for X-ray crystal structure analysis. As a result, it was found that Lovastatin was contained in the internal space of host molecule (ii), as shown in Figure 2. Furthermore, cocrystallizable molecule (iii) and 1,3,5-benzenetrimethanesulfonate were present between the two host molecules (ii). 【0157】 【0158】[Example 6] An aqueous solution of the nitrate of host molecule (i) (concentration 20 mM, 100 μL) was placed in a vial (diameter approximately 1 cm, volume 2.2 mL), and (1E,5E,9E)-cyclododec-1,5,9-triene and fluorantene (200 μg each) were added as guest molecules. The mixture was then stirred at 60°C for 30 minutes. The solid residue was removed using a disc filter, and the resulting solution was transferred to a vial of the same type. An aqueous solution of the cocrystallizable molecule (iv) (20 mM, 15 μL) was added, and the mixture was left to stand at 20°C for 12 hours, after which red crystals precipitated. One crystal was selected and subjected to X-ray single-crystal structure analysis. Figure 3 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 3, (1E,5E,9E)-cyclododec-1,5,9-triene and fluorantene are each housed in the internal space of host molecule (i). A cocrystallizable molecule (iv) was present between the two host molecules (i). 【0159】

Claims

1. A crystalline solid comprising a plurality of host molecules, a plurality of cocrystallizable molecules, and a plurality of guest molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls; each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecules and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them; each of the plurality of cocrystallizable molecules contained in the crystalline solid is interposed between two or three or more host molecules; and all or part of the plurality of host molecules contained in the crystalline solid contain the whole molecule or a part of the molecule of a guest molecule in their respective internal spaces.

2. The crystalline solid according to claim 1, wherein the host molecule is a polynuclear metal complex.

3. The crystalline solid according to claim 2, wherein the polynuclear metal complex comprises an ion of an element selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt, and a polydentate ligand having a π-conjugated system.

4. The polydentate ligand having the π-conjugated system is given by the following formula (1) The crystalline solid according to claim 3, wherein the ligand is represented as follows: (A is an aromatic m-valent group. X is a divalent organic group or a single bond directly connecting A and Y. Y is a coordinating atom or a monovalent group containing a coordinating atom. m represents an integer from 2 to 6. Multiple Xs may be different from each other, and multiple Ys may be different from each other.) 5. The crystalline solid according to claim 1, wherein the affinity interaction between the cocrystallizable molecule and the host molecule is one or more interactions selected from the group consisting of hydrophobic interactions, π-π interactions, CH-π interactions, and Coulomb interactions.

6. The crystalline solid according to claim 1, wherein the skeletal structure of the cocrystallizable molecule is non-planar.

7. The crystalline solid according to claim 6, wherein the nonplanar skeletal structure is due to one or more selected from the group consisting of rotational motion around a single bond, steric hindrance, a circular structure, an antiaromatic structure, and a nonplanar linkage structure.

8. The crystalline solid according to claim 1, wherein it is single-crystal.

9. The crystalline solid according to claim 1, which does not have single crystallinity.

10. An aggregate of crystalline solids according to claim 1.

11. A crystalline solid comprising a plurality of host molecules and a plurality of cocrystallizable molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecules and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them, each of the plurality of cocrystallizable molecules contained in the crystalline solid is interposed between two or three or more host molecules, and the plurality of host molecules contained in the crystalline solid are in a state in which they can accommodate a guest molecule in their respective internal spaces.

12. An aggregate of crystalline solids according to claim 11.

13. A method for producing a crystalline solid according to claim 1 using the crystalline solid according to claim 11, comprising the step (step a-I) of accommodating the crystalline solid according to claim 11 and a guest molecule in the same system, either in the presence or absence of a solvent, thereby accommodating the guest molecule in the internal space of all or some of the host molecules contained in the crystalline solid.

14. A method for producing a crystalline solid according to claim 1, using a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and linking structures connecting them, the method for producing a crystalline solid according to claim 1, comprising the steps of: preparing a solution containing the host molecule, the guest molecule, and the cocrystallizable molecule (step b-I); and precipitating a crystalline solid containing the host molecule containing the guest molecule and the cocrystallizable molecule from the solution obtained in step b-I (step b-II).

15. A method for producing a crystalline solid using a crystal holder, wherein the crystal holder has a crystal fixing portion and a shape that can be fixed directly or via other parts to a goniometer of a crystal structure analysis apparatus, and step b-II is performed with the solution obtained in step b-I in contact with the crystal fixing portion of the crystal holder, as described in claim 14.

16. A crystalline solid fabrication kit comprising a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures connecting them.

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