Material for forming x-ray structure analysis sample, and method for determining molecular structure of organic compound using same

Abstract

Provided is a novel material for forming an X-ray structure analysis sample of an organic compound.　A material for forming an X-ray structure analysis sample according to the present disclosure contains the metal complex crystal described below. Metal complex crystal: A metal complex crystal which is composed of a metal ion and a ligand that is coordinated to the metal ion. The metal complex crystal has a three-dimensional network structure that has regularly arranged vacancies, and the ligand includes a carboxylic acid-based ligand (c) and a pyridine-based ligand (p) in a combination of [I] or [II] described below. [I] A compound represented by formula (c1) and a compound represented by formula (p1) [II] A compound represented by formula (c2) and a compound represented by formula (p2)

Description

X-ray structural analysis sample forming material and method for determining molecular structure of organic compound using the same

[0001] The present disclosure relates to a novel material for forming a sample for X-ray structural analysis, and a method for determining the molecular structure of an organic compound using the material for forming a sample for X-ray structural analysis. This disclosure claims priority to Japanese Patent Application No. 2023-202754, filed in Japan on November 30, 2023, the contents of which are incorporated herein by reference.

[0002] As a method for determining the molecular structure of an organic compound, single crystal X-ray structural analysis, that is, a method in which a single crystal of an organic compound is subjected to X-ray structural analysis, is known. This method is very useful because it allows accurate determination of the molecular structure of an organic compound if a high-quality single crystal can be produced.

[0003] However, when the amount of organic compound is small, it is difficult to obtain a sufficient amount of single crystals, making it difficult to determine the molecular structure by this method. Also, there are organic compounds that are difficult to crystallize, and the above method cannot be used for such organic compounds.

[0004] Therefore, a crystalline sponge method has been developed that can determine the molecular structure of an organic compound by X-ray structural analysis without undergoing a process of crystallizing the organic compound (for example, see Patent Document 1). The crystalline sponge method uses a metal complex crystal having regularly aligned pores as a material for forming an X-ray structural analysis sample (or crystalline sponge), impregnates and fixes an organic compound whose molecular structure is desired to be determined into the pores of the metal complex crystal together with a solvent, and prepares the regularly aligned organic compound as a X-ray structural analysis sample (i.e., a sample to be subjected to X-ray structural analysis), and irradiates the obtained X-ray structural analysis sample with X-rays to determine the molecular structure of the organic compound.

[0005] Furthermore, Non-Patent Document 1 discloses that a metal complex crystal having regularly aligned pores can be obtained by reacting 1,3-bis(4-pyridylaminocarbonyl)benzene, 4,4'-dicarboxybiphenyl, and zinc nitrate hydrate. However, there is no disclosure of using the metal complex crystal as a material for forming a sample for X-ray structural analysis.

[0006] International Publication No. 2014 / 038220

[0007] Optimization of Reaction Conditions towards Multiple Types of Framework Isomers and Periodic-Increased Porosity: Luminescence Properties and Selective CO2 Adsorption over N2, ChemPhysChem, 2013, 14, 3594-3599.

[0008] When the metal complex crystal described in Patent Document 1 is used as a material for forming an X-ray structural analysis sample, the success rate of determining the molecular structure of an organic compound is about 30%, resulting in a low success rate. Furthermore, while the success rate of molecular structure determination can be increased by optimizing conditions such as the type of solvent used when impregnating the metal complex crystal with the organic compound and the impregnation temperature depending on the type of organic compound, the metal complex crystal described in Patent Document 1 has low solvent resistance and dissolves in medium- to high-polarity solvents, resulting in a limited number of solvents that can be used. Furthermore, the metal complex crystal described in Patent Document 1 has a hydrophobic environment within its pores, making it difficult to retain hydrophilic organic compounds within the pores, making it difficult to determine the molecular structure of hydrophilic organic compounds using the metal complex crystal. Furthermore, the metal complex crystal described in Patent Document 1 cannot maintain its crystal structure unless the pores are filled with a solvent. Therefore, the metal complex crystal cannot employ a technique in which the pores are filled with a gas containing a gaseous organic compound to immobilize the gaseous organic compound within the pores.

[0009] Therefore, an object of the present disclosure is to provide a novel material for preparing an X-ray structural analysis sample of an organic compound, which is capable of immobilizing organic compounds in an orderly aligned manner. Another object of the present disclosure is to provide a novel material for preparing an X-ray structural analysis sample of an organic compound, which is capable of immobilizing hydrophilic organic compounds in an orderly aligned manner. Another object of the present disclosure is to provide a novel material for preparing an X-ray structural analysis sample of an organic compound, which is capable of immobilizing gaseous organic compounds present in a gas in an orderly aligned manner. Another object of the present disclosure is to provide a method for determining the molecular structure of an organic compound using the material. Another object of the present disclosure is to provide a method for determining the molecular structure of an odor component using the material.

[0010] The present inventors conducted extensive research to solve the above-mentioned problems and discovered the following. Specifically, determining the molecular structure of an organic compound requires regularly aligned organic compounds. However, the metal complex crystal described in Patent Document 1 immobilizes organic compounds within pores through relatively weak intermolecular interactions, such as Π-Π interactions and σ-Π interactions, resulting in a low probability of retention within the pores. Furthermore, the metal complex crystal described in Patent Document 1 was found to have a low ability to regularly align organic compounds, resulting in a low probability of molecular structure determination when used as a crystalline sponge. On the other hand, amide groups can strongly interact with various functional groups through hydrogen bonds. Coordinating specific ligands containing amide groups to metal ions yields metal complex crystals with regularly aligned pores. The metal complex crystals thus obtained can accommodate organic compounds within the regularly aligned pores with a high probability. The accommodated organic compounds are firmly held in an oriented state. Therefore, using the metal complex crystals as a sample material for X-ray structural analysis allows for a high probability of determining the molecular structure of organic compounds by X-ray diffraction. The present disclosure has been completed based on these findings.

[0011] That is, the present disclosure provides a material for forming an X-ray structural analysis sample containing an organic compound in a regularly aligned state, the material comprising the following metal complex crystal: Metal complex crystal: A metal complex crystal composed of metal ions and ligands coordinated to the metal ions, the metal complex crystal having a three-dimensional network structure with regularly aligned pores, the ligands including a carboxylic acid-based ligand (c) and a pyridine-based ligand (p), the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) being a combination of [I] or [II] below: [I] A compound represented by the following formula (c1) and a compound represented by the following formula (p1): [II] A compound represented by the following formula (c2) and a compound represented by the following formula (p2): (In the formula, R １ , R ２ are the same or different and each represents a group selected from a single bond, a divalent hydrocarbon group, a divalent heterocyclic group, and a divalent group formed by linking two or more of the above groups. １ ~L ４ are the same or different and represent a single bond or a linking group.

[0012] The present disclosure also provides the material for forming a sample for X-ray structural analysis, wherein the metal ions are selected from zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions.

[0013] The present disclosure also provides the material for forming a sample for X-ray structural analysis, wherein the organic compound is an organic compound having a functional group that interacts with at least one group selected from a CONH group, a CO group, and an NH group.

[0014] The present disclosure also provides the material for forming a sample for X-ray structural analysis, wherein the organic compound is an organic compound having at least one functional group selected from a substituted or unsubstituted amino group, a carboxyl group, an active methylene group, a nitrile group, a ketone group, an aldehyde group, an ester group, an ether group, an amide group, a hydroxy group, a halogen group, and a sulfonamide group.

[0015] The present disclosure also provides the material for forming a sample for X-ray structural analysis, wherein the organic compound has a log P value of −5 or more and 7 or less.

[0016] The present disclosure also provides a method for determining the molecular structure of an organic compound (X), comprising the following steps 1 and 2: Step 1: impregnating the organic compound (X) into the X-ray structural analysis sample-forming material to fix the organic compound (X) in the pores of the X-ray structural analysis sample-forming material; and Step 2: irradiating the X-ray structural analysis sample-forming material with the fixed organic compound (X) with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the organic compound (X).

[0017] The present disclosure also provides a method for determining the molecular structure of a gaseous odor component (Y), comprising the following steps 1, 2, and 3. Step 1: Supplying a sample gas containing the gaseous odor component (Y) to a gas component separation column to separate the gaseous odor component (Y); Step 2: Permeating the separated gaseous odor component (Y) into the X-ray structural analysis sample formation material to fix the gaseous odor component (Y) in the pores of the X-ray structural analysis sample formation material; Step 3: Irradiating the X-ray structural analysis sample formation material to which the gaseous odor component (Y) has been fixed with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0018] The X-ray structural analysis sample forming material disclosed herein includes a metal complex crystal having regularly aligned large pores. The pores of the metal complex crystal are not fixed in shape but are flexible, deforming according to the shape of the organic compound (so-called guest molecule) incorporated. Therefore, various organic compounds can be incorporated into the pores of the metal complex crystal with a high probability. Furthermore, the metal complex crystal contains amide groups, which have the ability to form hydrogen bonds with various functional groups. Therefore, organic compounds incorporated into the pores of the metal complex crystal can be firmly fixed in a regularly aligned state with a high probability. Furthermore, the metal complex crystal contains amide groups, which create a hydrophilic environment within the pores, allowing hydrophilic organic compounds to be incorporated and fixed within the pores with a high probability. Furthermore, the metal complex crystal has excellent solvent resistance and can maintain its crystalline structure in various solvents. Furthermore, the metal complex crystal has excellent toughness and can maintain its crystalline structure whether the pores are filled with solvent or not (i.e., filled with air). Therefore, not only can a liquid organic compound (X) be infiltrated (or a solid organic compound (X) dissolved in a solvent be infiltrated) into the pores of the X-ray structural analysis specimen-forming material and immobilized, but also a gaseous organic compound (X) can be infiltrated and immobilized. Therefore, by using the X-ray structural analysis specimen-forming material, a solid, liquid, or gaseous organic compound (X) can be immobilized in the pores with a high probability, and the organic compound (X) can be regularly aligned within the metal complex crystal.

[0019] By using the X-ray structural analysis sample-forming material, even if the amount of organic compound (X) is too small to form a single crystal or if the compound is not capable of forming a single crystal, it can be regularly aligned within the pores of the X-ray structural analysis sample-forming material, and the X-ray structural analysis sample thus obtained can be subjected to X-ray structural analysis to determine the molecular structure of the organic compound (X). Therefore, the X-ray structural analysis sample-forming material is extremely useful as a means for determining the molecular structure of solid, liquid, or gaseous organic compounds (X) (especially hydrophilic organic compounds) by X-ray structural analysis.

[0020] Schematic diagram showing the crystal structure of sample-forming material 1 obtained in the example. Schematic diagram showing the crystal structure of sample-forming material 4 obtained in the comparative example. A schematic diagram of the crystal structure of the X-ray structural analysis sample obtained in Example 14 (a metal complex crystal with benzyl fixed in the pores) is shown in FIG. 3(a), a schematic diagram of the shape of the pores in the X-ray structural analysis sample is shown in FIG. 3(b), and a state in which the N-H constituting the amide group of sample-forming material 1 and the oxygen atom of the oxo group possessed by benzyl interact with each other is shown in FIG. 3(c). A schematic diagram of the crystal structure of the X-ray structural analysis sample obtained in Example 22 (a metal complex crystal with dibutyl fumarate fixed in the pores) is shown in FIG. 4(a), a schematic diagram of the shape of the pores in the X-ray structural analysis sample is shown in FIG. 4(b), and a state in which the N-H constituting the amide group of sample-forming material 1 and the oxygen atom of the oxo group possessed by dibutyl fumarate interact with each other is shown in FIG. 4(c). 1 is a schematic diagram showing an analytical device used in determining the structure of odorous components in Examples 1. The analytical device is equipped with a branching tool just before the detector of a gas chromatograph and is connected to a fraction collection device.

[0021] [X-ray structural analysis sample formation material] The X-ray structural analysis sample formation material (hereinafter sometimes referred to as "sample formation material") of the present disclosure is a material for forming a sample to be subjected to X-ray structural analysis, sometimes called a crystalline sponge, and is a material used to fix organic compounds in a regularly aligned state.

[0022] The sample-forming material contains at least the following metal complex crystal. The sample-forming material may contain other components, but the proportion of the following metal complex crystal in the total amount of the sample-forming material is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, particularly preferably 90% by weight or more, most preferably 95% by weight or more, and especially preferably 99% by weight or more. The sample-forming material may be composed essentially of the following metal complex crystal only.

[0023] (Metal Complex Crystal) The metal complex crystal is a metal complex crystal (preferably a microporous metal complex crystal) that is composed of metal ions and ligands that coordinate to the metal ions and has a three-dimensional network structure with regularly aligned pores.

[0024] The metal ions are not particularly limited as long as they can form a three-dimensional network structure by coordinate bonding with a ligand described below, and examples thereof include ions of metals in Groups 8 to 12 of the periodic table, such as zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions. Among these, divalent metal ions are preferred, and zinc ions and / or cobalt ions are particularly preferred, in that they can give metal complex crystals with a three-dimensional network structure having large pores.

[0025] The ligands include at least one type of carboxylic acid-based ligand (c) and at least one type of pyridine-based ligand (p). The combination of the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) is the following [I] or [II]: [I] A compound represented by the following formula (c1) and a compound represented by the following formula (p1): [II] A compound represented by the following formula (c2) and a compound represented by the following formula (p2):

[0026] (In the formula, R １ , R ２ are the same or different and each represents a group selected from a single bond, a divalent hydrocarbon group, a divalent heterocyclic group, and a divalent group formed by linking two or more of the above groups. １ ~L ４ are the same or different and represent a single bond or a linking group.

[0027] R １ , R ２Examples of the divalent hydrocarbon group in the formula (I) include linear or branched alkylene groups having 1 to 18 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene; 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene; cycloalkylene groups having 3 to 18 carbon atoms, such as a phenylene group (for example, an o-phenylene group, an m-phenylene group, or a p-phenylene group), a phenylenebis(methylene) group (for example, a 1,2-phenylenebis(methylene) group, a 1,3-phenylenebis(methylene) group, or a 1,4-phenylenebis(methylene) group), a biphenylene group, a naphthylene group, a binaphthylene group, an anthracenylene group, or a phenanthrylene group; ６－１４ Examples include an arylene group.

[0028] R １ , R ２ The divalent heterocyclic group in the formula (I) is a group obtained by removing two hydrogen atoms from the structural formula of a heterocycle. The heterocycle includes aromatic heterocycles and non-aromatic heterocycles. Examples of the heterocycle include 3- to 20-membered rings (preferably 3- to 10-membered rings, particularly preferably 4- to 6-membered rings) having carbon atoms and at least one heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.) as ring-constituting atoms, and condensed rings thereof.

[0029] Examples of heterocycles containing an oxygen atom as a heteroatom include three-membered rings such as an oxirane ring; four-membered rings such as an oxetane ring; five-membered rings such as a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, and a γ-butyrolactone ring; six-membered rings such as a 4-oxo-4H-pyran ring, a tetrahydropyran ring, and a morpholine ring; condensed rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-chromene ring, a chroman ring, and an isochroman ring; ４，８ ] undecan-2-one ring, 3-oxatricyclo[4.2.1.0 ４，８ ] Bridged rings such as nonan-2-one ring and the like are also included.

[0030] Examples of heterocyclic rings containing a sulfur atom as a heteroatom include five-membered rings such as a thiophene ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring; six-membered rings such as a 4-oxo-4H-thiopyran ring; and fused rings such as a benzothiophene ring.

[0031] Examples of heterocycles containing a nitrogen atom as a heteroatom include five-membered rings such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, and a triazole ring; six-membered rings such as an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, and a piperazine ring; and fused rings such as an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, and a purine ring.

[0032] L １ ~L ４ are the same or different and represent a single bond or a linking group. The linking group is a divalent group having one or more atoms, such as a divalent hydrocarbon group.

[0033] Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene; cycloalkylene groups having 3 to 18 carbon atoms, such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene; C alkylene groups such as phenylene groups (e.g., o-phenylene, m-phenylene, and p-phenylene), naphthylene groups (e.g., 1,3-naphthylene, 1,4-naphthylene, and 2,7-naphthylene), anthracenylene, and phenanthrylene groups; ６－１４ arylene groups; and groups in which two or more of these are linked together [for example, phenylenebis(methylene) groups (for example, 1,2-phenylenebis(methylene) groups, 1,3-phenylenebis(methylene) groups, 1,4-phenylenebis(methylene) groups), biphenylene groups, binaphthylene groups].

[0034] The divalent hydrocarbon group includes C ６－１４ an arylene group, or two or more of the arylene groups are each a single bond or C１－５ Groups linked via an alkylene group are preferred.

[0035] The benzene ring and pyridine ring in the formulae (c1), (p1), (c2) and (p2) may have a substituent other than the groups shown in the formulae.

[0036] Examples of the substituent include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (e.g., C １－４ alkoxy group), cyano group, nitro group, substituted or unsubstituted amino group (e.g., mono- or di-C such as methylamino group, dimethylamino group, ethylamino group, diethylamino group, etc. １－４ alkylamino groups; 5- to 8-membered cyclic amino groups such as 1-pyrrolidinyl, piperidino, and morpholino groups; C groups such as acetylamino, propionylamino, and benzoylamino groups; １－１０ acylamino group; sulfonylamino group such as benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), sulfonic acid group, alkyl group (for example, C groups such as methyl group, ethyl group, etc. １－４ alkyl groups), alkenyl groups (for example, vinyl groups, allyl groups, 1-butenyl groups, etc.) ２－４ alkenyl group), alkynyl group (e.g., ethynyl group, propynyl group, etc. ２－４ alkynyl group), C ３－８ cycloalkyl groups, aryl groups (e.g., C groups such as phenyl groups and naphthyl groups) ６－１０ aryl groups) and the like.

[0037] When the benzene ring or pyridine ring in the formulae (c1), (p1), (c2), and (p2) has two or more substituents, two groups selected from the substituents may be bonded to each other to form a ring.

[0038] Furthermore, the benzene ring or pyridine ring in the formulae (c1), (p1), (c2) and (p2) may be condensed with an aromatic or non-aromatic hydrocarbon ring or heterocyclic ring.

[0039] Specific examples of the compound represented by formula (c1) include compounds represented by the following formulas (c1-1) to (c1-4). The compound represented by formula (c1-1) below includes a compound represented by formula (c1-2) in which CONH-L in formula (c1) is a methyl group.１ Group and CONH-L ２ The same applies to the compounds represented by the following formulae (c1-2) to (c1-4).

[0040] As the compound represented by the formula (c1), the compound represented by the formula (c1-1) is preferred in that it gives a metal complex crystal having a three-dimensional network structure with large pores.

[0041] Specific examples of the compound represented by formula (p1) include compounds represented by the following formulas (p1-1) to (p1-7), such as R １ a compound in which a group corresponding to the group is bonded at the para position relative to the nitrogen atom of the pyridine ring, or a compound corresponding to the above compound, １ and compounds in which a group corresponding to the group is bonded to the ortho- or meta-position relative to the nitrogen atom of the pyridine ring.

[0042] As the compound represented by formula (p1), the compounds represented by formula (p1-1), formula (p1-2), formula (p1-5), and formula (p1-6) are preferred, in that metal complex crystals having a three-dimensional network structure with large pores can be obtained, and the compounds represented by formula (p1-1) and formula (p1-2) are particularly preferred.

[0043] Specific examples of the compound represented by formula (c2) include compounds represented by the following formulae (c2-1) to (c2-5). The compound represented by formula (c2-1) below includes a compound in which a carboxyl group is bonded at the ortho-, meta-, or para-position relative to the connecting portion of the benzene ring. The same applies to the compounds represented by formulae (c2-2) to (c2-5) below.

[0044] In the formula (c2-2), L represents a linking group. The linking group is a divalent group having one or more atoms, and examples thereof include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), an imino group (—NH—), a sulfonyl group (—S(═O) ２ -) etc.

[0045] As the compound represented by formula (c2), the compound represented by formula (c2-1) and the compound represented by formula (c2-2) are preferred, and the compound represented by formula (c2-1) is particularly preferred, in that a metal complex crystal having a three-dimensional network structure with large pores can be obtained.

[0046] Specific examples of the compound represented by formula (p2) include compounds represented by the following formulas (p2-1) to (p2-4). The compound represented by formula (p2-1) below includes a compound represented by formula (p2-1) below, wherein CONH-L in formula (p2) is a methyl group; ３ Group and CONH-L ４ The same applies to compounds represented by the following formulae (p2-2) to (p2-4).

[0047] As the compound represented by the formula (p2), the compound represented by the formula (p2-1) is preferred in that it gives a metal complex crystal having a three-dimensional network structure with large pores.

[0048] The ligands constituting the metal complex crystal include a carboxylic acid ligand (c) and a pyridine ligand (p), and the content ratio of the carboxylic acid ligand (c) to the pyridine ligand (p) [carboxylic acid ligand (c) / pyridine ligand (p); molar ratio] is, for example, 30 / 70 to 70 / 30, and is preferably 40 / 60 to 60 / 40, particularly preferably 45 / 55 to 55 / 45, in that a metal complex crystal having a three-dimensional network structure with large pores can be obtained.

[0049] The content ratio of the metal ion to the carboxylic acid ligand (c) [metal ion / carboxylic acid ligand (c); molar ratio] is, for example, 30 / 70 to 70 / 30, preferably 40 / 60 to 60 / 40, and particularly preferably 45 / 55 to 55 / 45.

[0050] The content ratio of the metal ion to the pyridine-based ligand (p) [metal ion / pyridine-based ligand (p); molar ratio] is, for example, 30 / 70 to 70 / 30, preferably 40 / 60 to 60 / 40, and particularly preferably 45 / 55 to 55 / 45.

[0051] The ligand may contain other ligands in addition to the carboxylic acid-based ligand (c) and the pyridine-based ligand (p). Examples of the other ligands include F － , Cl － ,Br － , I － , SCN － , NO ３ － , ClO ４ － , B.F. ４ － , SbF ４ － , P.F. ６ － , AsF ６ － , C.H. ３ COO － Examples of anions include:

[0052] As the anion, NO is preferred because it can produce a metal complex crystal with a three-dimensional network structure having large pores. ３ － , F － , Cl － ,Br － , and I － Preferred are anions selected from NO ３ － is particularly preferred.

[0053] The proportion of the total content of the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) in the total amount of ligands constituting the metal complex crystal is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

[0054] The metal complex crystal has a three-dimensional network structure with regularly arranged pores. The pores are spaces present inside the metal complex crystal and are partitioned by a network structure composed of metal ions and ligands.

[0055] The pores are preferably arranged three-dimensionally and regularly without disorder to the extent that they can be confirmed by X-ray structural analysis.

[0056] The shape of the pores is not particularly limited, but it is preferable that each pore has a uniform shape and a uniform size to the extent that it can be confirmed by X-ray structural analysis.

[0057] The shape of the pores is variable depending on the shape of the organic compound (X) incorporated into the pores, because the metal complex crystal is not composed of a series of three-dimensional network structures, but rather is composed of a plurality of (e.g., three or more, preferably four or more) independent three-dimensional network structures interpenetrating each other.

[0058] The size of the pores present in one unit cell is preferably large enough to encapsulate one to several (for example, 1 to 6) organic compounds (X).

[0059] The size of the vacancy correlates with the diameter of the inscribed circle of the vacancy (hereinafter sometimes simply referred to as the "inscribed circle of the vacancy") in a plane parallel to the crystal plane that is closest to perpendicular to the direction in which the vacancy extends (hereinafter sometimes referred to as the "parallel plane"). The larger the inscribed circle, the larger the vacancy, and the smaller the inscribed circle, the smaller the vacancy.

[0060] The "direction in which the vacancy extends" can be determined by the following method. First, a crystal plane 1 (one of six crystal planes connecting four lattice points contained in one unit cell) is selected in an appropriate direction that intersects the target vacancy. Then, atoms that constitute the metal complex crystal and are present on crystal plane 1 are represented using van der Waals radii, and a cross-sectional view of the vacancy is drawn, with crystal plane 1 as the cutting plane. Similarly, a cross-sectional view of the vacancy is drawn, with crystal plane 2, which is shifted by one unit cell from crystal plane 1, as the cutting plane. Next, a straight line is drawn in the three-dimensional diagram to connect the centers of the cross-sectional shapes of the vacancies on each crystal plane. The direction of the line obtained at this time is the direction in which the vacancy extends.

[0061] The "diameter of the inscribed circle of the hole" can be determined by the following method. First, a cross-sectional view of the hole is drawn using the method described above. Next, an inscribed circle is drawn on the cross-sectional view, the diameter of the inscribed circle is measured, and the obtained measurement value is converted to an actual scale, thereby determining the actual diameter of the inscribed circle of the hole. Furthermore, by gradually translating the parallel planes within one unit cell, cross-sectional views of the hole on each parallel plane are drawn, and the diameter of the inscribed circle is measured, thereby determining the diameter of the inscribed circle at the narrowest part and the diameter of the inscribed circle at the widest part.

[0062] The diameter of the inscribed circle of the pore is, for example, 8 to 12 Å, preferably 9 to 12 Å.

[0063] Furthermore, when the shape of the pores is significantly different from a perfect circle, it is preferable to predict the size of the pores from the minor axis and major axis of the inscribed ellipse of the pores in the parallel plane.

[0064] The major axis of the inscribed ellipse of the pore is preferably 10 to 15 Å, more preferably 10 to 12 Å, and the minor axis of the inscribed ellipse of the pore is preferably 8 to 15 Å, more preferably 8 to 11 Å.

[0065] The metal complex crystal contains a ligand having an amide group (CONH) as a constituent element, and the amide group (CONH group) and the CO group and NH group that constitute the amide group can interact with various functional groups via hydrogen bonds. Therefore, the metal complex crystal can determine the molecular structure of a wide range of organic compounds, or a large number of organic compounds. Furthermore, the metal complex crystal can firmly fix organic compounds within the pores through hydrogen bonds with the amide group, CO group, or NH group. Therefore, by using the metal complex crystal, it is possible to determine with a high probability the molecular structures of various organic compounds that have functional groups that interact with amide groups, CO groups, or NH groups.

[0066] Furthermore, the metal complex crystal has excellent durability and can maintain its crystal structure not only in a solution but also in an air atmosphere. Therefore, the metal complex crystal can capture and fix volatile organic compounds that are gasified and dispersed in the gas phase into the pores of the metal complex crystal. Therefore, the metal complex crystal can be used to penetrate and fix odor components in a gaseous state, and can also be used to determine their molecular structure, making it highly versatile.

[0067] [Method for Producing a Material for Forming a Sample for X-ray Structural Analysis] The material for forming a sample for X-ray structural analysis can be produced by utilizing the following method for producing a metal complex crystal.

[0068] (Method for producing metal complex crystal) The metal complex crystal can be produced, for example, by reacting a carboxylic acid-based ligand (c), a pyridine-based ligand (p), and a salt of a metal ion and a counter ion (hereinafter, sometimes referred to as a "metal salt") in the presence of a solvent.

[0069] Examples of the counter ion include F － , Cl － ,Br － , I － , SCN － , NO ３ － , ClO ４ － , B.F. ４ － , SbF ４ －, P.F. ６ － , AsF ６ － , C.H. ３ COO － Examples of anions include:

[0070] The molar ratio of the carboxylic acid ligand (c) to the pyridine ligand (p) is, for example, 30 / 70 to 70 / 30. The molar ratio is preferably 40 / 60 to 60 / 40, particularly preferably 45 / 55 to 55 / 45, in order to obtain a metal complex crystal having a three-dimensional network structure with large pores.

[0071] The amount of the metal salt used is, for example, 0.2 to 3 moles, preferably 0.5 to 2 moles, and particularly preferably 0.8 to 1.5 moles per mole of the carboxylic acid ligand (c) or pyridine ligand (p).

[0072] Examples of the solvent include water; benzene; toluene, xylene, ethylbenzene, trifluoromethylbenzene (or trifluorotoluene), chlorobenzene, anisole, benzonitrile, nitrobenzene, ethyl benzoate, and other benzene derivatives in which at least one hydrogen atom bonded to the benzene ring is substituted with a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a cyano group, a nitro group, a substituted oxycarbonyl group, or the like; aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; haloalkanes such as carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; chain or cyclic ethers such as diethyl ether, dibutyl ether, dimethoxyethane, dioxane, and tetrahydrofuran; and organic acids such as acetic acid. These may be used alone or in combination of two or more.

[0073] Among these, a mixture of water and an amide (particularly, DMF) is preferred as the solvent. The volume ratio of water to the total volume of water and the amide is, for example, 5 to 95 vol%. In order to obtain a metal complex crystal having a three-dimensional network structure with large pores, the lower limit of the volume ratio is preferably 10 vol%, particularly preferably 15 vol%, and the upper limit of the volume ratio is preferably 80 vol%, particularly preferably 60 vol%, more preferably 50 vol%, even more preferably 40 vol%, particularly preferably 30 vol%, most preferably 25 vol%, and particularly preferably 17 vol%.

[0074] The reaction temperature is, for example, 60 to 150°C, preferably 80 to 120°C, and particularly preferably 90 to 110°C.

[0075] The reaction time is, for example, 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 2 to 6 hours, and most preferably 3 to 5 hours.

[0076] The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.

[0077] After the reaction is completed, the resulting reaction product may be separated and purified by common methods such as precipitation, washing and filtration.

[0078] [Method for Determining the Molecular Structure of Organic Compound (X)] The method for determining the molecular structure of organic compound (X) includes the following steps 1 and 2. Step 1: Permeating the organic compound (X) into the sample-forming material (or the metal complex crystal) to fix the organic compound (X) in the pores of the sample-forming material (or the metal complex crystal). Step 2: Irradiating the sample-forming material (or the metal complex crystal) to which the organic compound (X) has been fixed with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the organic compound (X).

[0079] The organic compound (X) is, for example, a compound having at least one functional group that interacts via hydrogen bonding with an amide group (CONH group) contained in the sample-forming material (or the metal complex crystal) or with a CO group or NH group constituting the amide group.

[0080] Examples of the functional group that interacts with at least one group selected from the group consisting of a CONH group, a CO group, and an NH group include groups having an electronegativity of 1.0 to 4.0 (preferably 1.6 to 3.6, particularly preferably 2.0 to 3.4).

[0081] Examples of the functional group include a substituted or unsubstituted amino group, a carboxyl group, an active methylene group, a nitrile group, a ketone group, an aldehyde group, an ester group, an ether group, an amide group, a hydroxy group, a halogen group, and a sulfonamide group.

[0082] The molecular weight of the organic compound (X) is, for example, 1,000 or less, preferably 800 or less, and particularly preferably 600 or less. The lower limit of the molecular weight of the organic compound (X) is, for example, 15, preferably 30, and particularly preferably 50.

[0083] The organic compound (X) is preferably a hydrophilic compound, and the log P (octanol / water partition coefficient) value of the organic compound (X) is, for example, from −5 to 7. In terms of improving the determination rate of the molecular structure, the lower limit of the log P is preferably −3, particularly preferably −1, and the upper limit of the log P is preferably 6, particularly preferably 5, most preferably 4.5, and particularly preferably 3. The log P value of the organic compound (X) can be determined using commercially available software (for example, the software "EPI suite" jointly developed by the U.S. EPA (The Estimations Programs Interface for Windows) and Syracuse).

[0084] (Step 1) Step 1 is a step of impregnating the sample-forming material with an organic compound (X) to fix the organic compound (X) in the pores of the sample-forming material.

[0085] As the sample forming material, it is preferable to select and use from among the metal complex crystals obtained by the above-mentioned method for producing metal complex crystals those that have excellent transparency and a clear external shape (shape, for example, needle-like, block-like, thin flake-like, etc.) in order to improve the determination rate of the molecular structure.

[0086] When the sample-forming material is needle-shaped or block-shaped, the length of the sample-forming material is, for example, 10 μm or more, preferably 10 to 200 μm, and particularly preferably 10 to 100 μm. If the sample-forming material is too small, the measurement time tends to be long, while if the sample-forming material is too large, it becomes difficult to sufficiently penetrate the organic compound (X), and the determination rate of the molecular structure tends to decrease.

[0087] The amount of the sample forming material used is, for example, 0.1 to 50 mg, preferably 0.5 to 15 mg, and particularly preferably 1 to 3 mg.

[0088] The metal complex crystal constituting the sample-forming material has excellent toughness, and therefore the pores of the metal complex crystal may or may not be filled with a solvent.

[0089] The method for permeating the organic compound (X) into the sample-forming material and fixing the organic compound (X) in the pores of the sample-forming material can be appropriately selected depending on the state (liquid, gas, or solid) of the organic compound (X).

[0090] When the organic compound (X) is a liquid, the immobilization method may include placing the sample-forming material in a container such as a test tube, adding the organic compound (X) thereto, and allowing the mixture to stand at −20 to 100° C. for 0.25 to 24 hours.

[0091] When the organic compound (X) is a gas, the immobilization method may include filling a sealed container such as a capped test tube with an inert gas (e.g., helium gas, nitrogen gas, etc.), sealing the sample-forming material and the organic compound (X) therein, and allowing the mixture to stand for 0.25 to 24 hours at −20 to 100° C. Furthermore, before sealing the mixture in the sealed container, the sample gas containing the gaseous organic compound (X) may be subjected to a separation treatment such as gas chromatography to increase the concentration of the organic compound (X).

[0092] When the organic compound (X) is a solid, the immobilization method may include placing the sample-forming material in a container such as a test tube, adding a solution of the organic compound (X) dissolved in a solvent inert to the organic compound (X) (hereinafter, sometimes referred to as an "inert solvent"), and allowing the solution to stand at -20 to 100°C for 0.25 to 24 hours. After the standing, the infiltrated solution may be concentrated. By performing the concentration treatment, the immobilization rate of the organic compound (X) in the pores is increased, and the determination rate of the molecular structure is improved.

[0093] The sample-forming material has excellent solvent resistance and can maintain its crystalline structure in various solvents. Therefore, a solvent that improves the determination rate of the molecular structure can be selected from among inert solvents and used. Examples of the inert solvent include alcohols such as methanol, ethanol, and isopropyl alcohol; and linear or cyclic ethers such as tetrahydrofuran (THF), dimethoxyethane, and dioxane. These can be used alone or in combination of two or more.

[0094] The concentration of the organic compound (X) in the solution obtained by dissolving the organic compound (X) in an inert solvent is, for example, 0.001 to 50 μg / μL, preferably 0.01 to 5 μg / μL, and more preferably 0.1 to 1 μg / μL.

[0095] Since the sample-forming material has an amide group, when an organic compound (X) is permeated into the sample-forming material, the organic compound (X) taken up into the pores of the sample-forming material can be firmly fixed by hydrogen bonding.

[0096] Through this step, an X-ray structural analysis sample is obtained in which the organic compound (X) is fixed in the pores of the sample-forming material.

[0097] (Step 2) Step 2 is a step of irradiating the X-ray structural analysis sample obtained in the previous step (i.e., the sample in which the organic compound (X) is fixed in the pores of the sample-forming material) with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the organic compound (X).

[0098] In the method for determining the molecular structure of organic compound (X), there is no need to go through a process of crystallizing organic compound (X). Therefore, even if the amount of organic compound (X) is too small to obtain a single crystal, or even if organic compound (X) is a compound that cannot be crystallized into a single crystal, the molecular structure can be determined by X-ray structural analysis.

[0099] Furthermore, according to the method for determining the molecular structure of the organic compound (X), the molecular structure of the organic compound (X) can be determined by X-ray structural analysis even when the organic compound (X) is in a gaseous state.

[0100] Therefore, according to the method for determining the molecular structure of organic compound (X), the structures of trace impurities in pharmaceuticals, odor-causing substances (including odors) (e.g., fragrances), food additives, trace components in plants and animals, etc. can be easily determined.

[0101] [Method for determining the molecular structure of gaseous odor component (Y)] The method for determining the molecular structure of gaseous odor component (Y) comprises the following steps 1, 2, and 3. Step 1: Supply a sample gas containing gaseous odor component (Y) to a gas component separation column to separate the gaseous odor component (Y). Step 2: Permeate the separated gaseous odor component (Y) into the sample-forming material (or the metal complex crystal) to fix the gaseous odor component (Y) in the pores of the sample-forming material (or the metal complex crystal). Step 3: Irradiate the sample-forming material (or the metal complex crystal) to which the gaseous odor component (Y) has been fixed with X-rays, and analyze the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0102] (Step 1) Step 1 is a step of supplying a sample gas containing the gaseous odor component (Y) to a gas component separation column and separating the gaseous odor component (Y). Step 1 is a step of supplying a sample gas containing the gaseous odor component (Y) together with a carrier gas to a gas component separation column and separating the gaseous odor component (Y) together with the carrier gas.

[0103] The gaseous odorous component (Y) is a gaseous organic compound that emits an odor, and is preferably a compound having the same functional group and molecular weight as the organic compound (X).

[0104] The sample gas may contain two or more odor components (Y1, Y2, . . . , Yn; n is an integer of 2 or more), and may further contain gas components other than odor components.

[0105] A gas component separation column has a stationary phase inside, and when a sample gas containing multiple components is supplied into the column together with a carrier gas, the components in the sample gas interact differently with the stationary phase, resulting in different retention times. The carrier gas is preferably an inert gas such as helium gas or nitrogen gas.

[0106] The column may be connected to a device for collecting the sample gas separated by the column.

[0107] When the sample gas contains two or more gaseous odor components (Y1, Y2, ..., Yn; n is an integer of 2 or more), it is preferable to separate the gaseous odor component (Y1), the gaseous odor component (Y2), ..., and the gaseous odor component (Yn). The gaseous odor components may also be separated together with a carrier gas.

[0108] (Step 2) Step 2 is a step of permeating the gaseous odor component (Y) fractionated in step 1 into the sample formation material to fix the gaseous odor component (Y) in the pores of the sample formation material.

[0109] This step can be carried out in the same manner as in step 1 of the method for determining the molecular structure of the organic compound (X). Through this step, a sample for X-ray structural analysis can be obtained, in which the gaseous odorous component (Y) is fixed in the pores of the metal complex crystal.

[0110] (Step 3) Step 3 is a step of irradiating the X-ray structural analysis sample obtained in the previous step (i.e., the sample in which the gaseous odor component (Y) is fixed in the pores of the sample-forming material) with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0111] This step can be carried out in the same manner as step 2 of the method for determining the molecular structure of the organic compound (X).

[0112] According to the method for determining the molecular structure of gaseous odor component (Y), the gaseous odor component (Y) can be fixed to a sample-forming material while still in a gaseous state to form a sample for X-ray structural analysis, and the molecular structure can be easily determined by subjecting the formed X-ray structural analysis sample to X-ray structural analysis. Furthermore, with regard to substances that cause odors (including scents), odor components have traditionally been identified by sniffing GC-MS, relying on human senses, but according to the method for determining the molecular structure of gaseous odor component (Y), the molecular structure of the gaseous odor component (Y) can be accurately identified without relying on human senses.

[0113] The above-described configurations and combinations thereof of the present disclosure are merely examples, and additions, omissions, substitutions, and modifications of the configurations are possible as appropriate without departing from the spirit of the present disclosure. Furthermore, each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Furthermore, the present disclosure is not limited by the embodiments.

[0114] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples.

[0115] The single crystal X-ray structure analysis was carried out using the following automatic single crystal X-ray diffractometer: Automatic single crystal X-ray diffractometer: "XtaLABSynergy Custom" manufactured by Rigaku Corporation; Radiation source: Cu-Kα ray (wavelength 0.79 Å); Output: 50 mA, 24 kV

[0116] Example 1 (Production of an X-ray structural analysis sample forming material containing DMF and water in the pores) A ​​carboxylic acid-based ligand (24.2 mg, 0.1 mol) represented by the following formula (c2-1-1), a pyridine-based ligand (31.8 mg, 0.1 mol) represented by the following formula (p2-1), and Zn(NO ３ ) ２ 6H ２ O (29.7 mg, 0.1 mol) and DMF / H ２ A mixed solvent of DMF / H2O (4 mL / 1 mL) was added and sonicated to dissolve the compound. The test tube was then tightly capped and allowed to stand at 100°C for 6 hours. The solvent in the test tube was removed using a Pasteur pipette, and fresh DMF / H2O was added.２ The process of replacing the solvent with a mixed solvent of 0 (4 mL / 1 mL) was repeated three times.

[0117]

[0118] This resulted in transparent, needle-like or block-like single crystal particles measuring 10 to 200 μm in length. These were designated as sample-forming material 1. Sample-forming material 1 contains DMF and water within its pores. Single-crystal X-ray structural analysis of the obtained sample-forming material 1 was performed to confirm the crystal structure. A schematic diagram of sample-forming material 1 is shown in Figure 1.

[0119] Single crystal X-ray structural analysis confirmed that the specimen-forming material 1 had a three-dimensional network structure. It was also found that the inscribed ellipse of the void contained in the specimen-forming material 1 had a major axis of 12 Å and a minor axis of 8 Å.

[0120] Example 2 (Production of X-ray structural analysis sample forming material 2 containing ethyl acetate in the pores) ２ The solvent was removed from a screw-cap test tube containing 0 (4 mL / 1 mL) and sample-forming material 1 containing DMF in its pores, and replaced with an ethyl acetate / DMF (1 mL / 4 mL) mixed solvent and allowed to stand for one day. The solvent in the test tube was then removed and replaced with an ethyl acetate / DMF (1 mL / 2 mL) mixed solvent and allowed to stand for one day. The solvent in the test tube was then removed and replaced with an ethyl acetate / DMF (1 mL / 1 mL) mixed solvent and allowed to stand for one day. The solvent in the test tube was then removed and replaced with an ethyl acetate / DMF (2 mL / 1 mL) mixed solvent and allowed to stand for one day. This process of removing the solvent from the test tube and replacing it with ethyl acetate was repeated three times. This resulted in needle- or block-shaped single-crystal particles containing ethyl acetate in their pores. This was designated sample-forming material 2. Sample-forming material 2 contains ethyl acetate in its pores. Single-crystal X-ray structural analysis of the obtained sample-forming material 2 confirmed a three-dimensional network structure similar to that of sample-forming material 1.

[0121] Example 3 (Preparation of X-ray structural analysis sample-forming material 3 containing THF in its pores) The solvent was removed from a screw-cap test tube containing ethyl acetate and sample-forming material 2 containing ethyl acetate in its pores, obtained in the same manner as in Example 2, and replaced with a THF / ethyl acetate (1 mL / 4 mL) mixed solvent and allowed to stand for one day. The solvent in the test tube was then removed and replaced with a THF / ethyl acetate (1 mL / 2 mL) mixed solvent and allowed to stand for one day. The solvent in the test tube was then removed and replaced with a THF / ethyl acetate (1 mL / 1 mL) mixed solvent and allowed to stand for one day. The solvent in the test tube was then removed and replaced with a THF / ethyl acetate (2 mL / 1 mL) mixed solvent and allowed to stand for one day. This process of removing the solvent from the test tube and replacing it with THF was repeated three times. This resulted in needle-shaped or block-shaped single-crystal particles containing THF in their pores. This was designated sample-forming material 3. Sample-forming material 3 contains THF in its pores. When the obtained specimen-forming material 3 was subjected to single crystal X-ray structural analysis, a three-dimensional network structure similar to that of specimen-forming material 1 was confirmed.

[0122] Comparative Example 1 (Production of X-ray structural analysis sample forming material 4) First, 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) (31.3 mg, 0.1 mmol), CHCl ３ 21 mL of zinc chloride and 1.7 mL of methanol were added and sonicated to completely dissolve them. 4.5 mL of the resulting solution was placed in a screw-cap test tube. Next, zinc chloride (20.5 mg, 0.15 mmol) and 5 mL of methanol were added to a 10 mL vial and sonicated to dissolve them. 1 mL of the resulting solution was added to the screw-cap test tube. The screw-cap test tube was then capped and allowed to stand at room temperature for 3 days. This resulted in transparent, needle-shaped or block-shaped single-crystal particles measuring 10 to 200 μm in length. This was designated Sample Formation Material 4.

[0123] Single crystal X-ray structural analysis was performed on the sample-forming material 4. A schematic diagram of the sample-forming material 4 is shown in Figure 2. From the single crystal X-ray structural analysis, it was found that the inscribed ellipse of the void contained in the sample-forming material 4 had a major axis of 13 Å and a minor axis of 10 Å.

[0124] Evaluation of Solvent Resistance The solvent resistance of sample-forming material 1 obtained in Example 1 and sample-forming material 4 obtained in Comparative Example 1 was evaluated by the following method. That is, one single crystal particle of the sample-forming material was placed in a microvial, 1 μL of the following solvent was added thereto, and the mixture was left to stand at 50° C. or room temperature (25° C.) for 17 hours. After standing, it was visually observed whether the crystalline structure was maintained. Then, the solvent resistance was evaluated according to the following criteria. <Solvent Resistance Evaluation Criteria> Excellent (○): The crystalline structure was maintained, and single-crystal X-ray measurement was performed to observe the skeleton of the metal complex. Good (Δ): The crystalline structure was not maintained when left to stand at 50° C. for 17 hours, but the crystalline structure was maintained when left to stand at room temperature for 17 hours. Poor (×): The crystalline structure was not maintained.

[0125]

[0126] Example 11 (Structure determination of organic compound having a ketone group) 45 μL of THF was placed in a microvial with a septum cap, and then one single crystal particle of the sample forming material 1 containing DMF obtained in Example 1 was immersed in the THF. Thereafter, as much THF as possible was removed using a pipette.

[0127] Next, 1 μg of 4-methylacetophenone was added to the microvial. Thereafter, the microvial was capped and allowed to stand in a constant temperature room at 50°C for 17 hours. Thereafter, sample forming material 1 was removed from the microvial. Sample forming material 1 removed from the microvial was used as the sample for X-ray structural analysis.

[0128] The obtained X-ray structure analysis sample was mounted on an X-ray structure analyzer, and crystal structure analysis was performed. The crystal structure analysis ability was evaluated according to the following evaluation criteria. The results are shown in the table below. <Evaluation criteria for crystal structure analysis ability> ◎ (Good): The molecular structure could be determined very clearly. ○ (Fair): The molecular structure could be determined with a certain degree of accuracy. × (Fail): The molecular structure could not be determined.

[0129] Examples 12 to 14 (Structure Determination of Organic Compound Having Ketone Group) The same procedure as in Example 11 was carried out, except that organic compound (X) shown in Table 2 below was used instead of 4-methylacetophenone. The results are shown in the table below. Furthermore, a schematic diagram of the crystal structure of the X-ray structural analysis sample (metal complex crystal with benzyl fixed in the pores) obtained in Example 14 is shown in FIG. 3(a), a schematic diagram of the shape of the pores in the X-ray structural analysis sample is shown in FIG. 3(b), and the interaction between the N-H constituting the amide group of sample-forming material 1 and the oxygen atom of the oxo group of benzyl is shown in FIG. 3(c).

[0130] Comparative Examples 11 to 14 (Structure determination of organic compounds having a ketone group) The same procedures as in Examples 11 to 14 were carried out except that sample forming material 4 was used instead of sample forming material 1. The results are shown in the table below.

[0131]

[0132] Examples 15 to 27 and Comparative Examples 15 to 27: X-ray structural analysis samples were obtained and subjected to crystal structure analysis in the same manner as in Example 11, except that organic compounds (X) listed in Tables 3 to 5 below were used instead of 4-methylacetophenone. The results are shown in the tables below. A schematic diagram of the crystal structure of the X-ray structural analysis sample (metal complex crystal with dibutyl fumarate fixed in the pores) obtained in Example 22 is shown in FIG. 4(a), a schematic diagram of the shape of the pores in the X-ray structural analysis sample is shown in FIG. 4(b), and the interaction between the N-H constituting the amide group of sample-forming material 1 and the oxygen atom of the oxo group in dibutyl fumarate is shown in FIG. 4(c).

[0133]

[0134]

[0135]

[0136] Example 28 (Structure Determination of Odor Component) 5 mL of the gas phase of bottled nitrobenzene was aspirated with a syringe and collected, and this was designated as gaseous odor component (Y). The collected gaseous odor component (Y) was added to a capped vial containing one single crystal particle of sample-forming material 1, and allowed to stand at 50°C for 2 hours. Thereafter, sample-forming material 1 was removed from the vial, and this was designated as the X-ray structural analysis sample. The obtained X-ray structural analysis sample was mounted on an X-ray structural analysis device and subjected to crystal structural analysis, and the overall molecular structure was determined from the X-ray diffraction photograph.

[0137] Example 29 (Structure Determination of Odor Component) A sample solution was obtained by dissolving 5 mg of nitrobenzene, an odor component, in 1 mL of acetone. 5 μL of the resulting sample solution was injected through inlet 2 of a gas chromatograph fractionator (specified below). The components that passed through column 3 were taken into fractionator 6 via the branching section, and fractionated into six fractionator tubes 7 (fractionator tubes cooled to -70°C) containing a single single crystal particle of sample-forming material 1. The fractionator tubes were then cooled to 50°C for 17 hours (see FIG. 5). Sample-forming material 1 from fractionator tube 7 was then removed and used as a sample for X-ray structural analysis. The resulting X-ray structural analysis sample was mounted on an X-ray structural analysis device and subjected to crystal structural analysis. The overall molecular structure was determined from X-ray diffraction images.

[0138] <Gas chromatograph fractionation apparatus specifications> Gas chromatograph fractionation apparatus: Product name "VPS-2800", manufactured by GL Sciences Inc. Column: DB-5MS 30 m - 0.32 mm - 0.5 μm, manufactured by GL Sciences Inc. Column heating temperature: 80°C (0 min) → 2°C / min → 140°C (0 min) Carrier gas: Helium Column flow rate: 6.58 mL / min

[0139] Example 30 (Structure determination of odorous components) The same procedure as in Example 29 was carried out except that α-terpineol was used instead of nitrobenzene. As a result, the molecular structure of α-terpineol could be determined from the X-ray diffraction photograph.

[0140] Example 31 (Determination of the Structure of Odor Components) The same procedure as in Example 29 was carried out except that eugenol was used instead of nitrobenzene. As a result, the molecular structure of eugenol could be determined from the X-ray diffraction photograph.

[0141] In summary, the configuration of the present disclosure and its variations are described below. [1] A material for forming an X-ray structural analysis sample containing an organic compound in a regularly aligned state, the material comprising the following metal complex crystal: Metal complex crystal: A metal complex crystal composed of metal ions and ligands coordinated to the metal ions, the metal complex crystal having a three-dimensional network structure with regularly aligned pores, the ligands including a carboxylic acid-based ligand (c) and a pyridine-based ligand (p), the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) being a combination of [I] or [II] below: [I] A compound represented by formula (c1) and a compound represented by formula (p1); [II] A compound represented by formula (c2) and a compound represented by formula (p2); [2] The material for forming an X-ray structural analysis sample according to [1], wherein the metal ions are selected from zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions. [3] The X-ray structural analysis sample forming material according to [1] or [2], wherein the organic compound is an organic compound having a functional group that interacts with at least one group selected from a CONH group, a CO group, and an NH group. [4] The X-ray structural analysis sample forming material according to [1] or [2], wherein the organic compound is an organic compound having at least one functional group selected from a substituted or unsubstituted amino group, a carboxyl group, an active methylene group, a nitrile group, a ketone group, an aldehyde group, an ester group, an ether group, an amide group, a hydroxy group, a halogen group, and a sulfonamide group. [5] The X-ray structural analysis sample forming material according to any one of [1] to [4], wherein the organic compound has a log P value of -5 or more and 7 or less. [6] The X-ray structural analysis sample forming material according to any one of [1] to [5], wherein the compound represented by formula (c1) in [I] is at least one compound selected from the compounds represented by formulas (c1-1) to (c1-4). [7] The material for forming an X-ray structural analysis sample according to any one of [1] to [5], wherein the compound represented by formula (c1) in [I] is a compound represented by formula (c1-1).[8] The X-ray structural analysis sample forming material according to any one of [1] to [7], wherein the compound represented by formula (p1) in [I] is at least one compound selected from the compounds represented by formulas (p1-1) to (p1-7). [9] The X-ray structural analysis sample forming material according to any one of [1] to [7], wherein the compound represented by formula (p1) in [I] is at least one compound selected from the compounds represented by formulas (p1-1), (p1-2), (p1-5), and (p1-6).

[10] The X-ray structural analysis sample forming material according to any one of [1] to [7], wherein the compound represented by formula (p1) in [I] is a compound represented by formula (p1-1) and / or a compound represented by formula (p1-2).

[11] The X-ray structural analysis sample forming material according to any one of [1] to

[10] , wherein the compound represented by formula (c2) in [II] is at least one compound selected from the compounds represented by formulas (c2-1) to (c2-5).

[12] The X-ray structural analysis sample forming material according to any one of [1] to

[10] , wherein the compound represented by formula (c2) in [II] is a compound represented by formula (c2-1) and / or a compound represented by formula (c2-2).

[13] The X-ray structural analysis sample forming material according to any one of [1] to

[10] , wherein the compound represented by formula (c2) in [II] is a compound represented by formula (c2-1).

[14] The X-ray structural analysis sample forming material according to any one of [1] to

[13] , wherein the compound represented by formula (p2) in [II] is at least one compound selected from the compounds represented by formulas (p2-1) to (p2-4).

[15] The material for forming an X-ray structural analysis sample according to any one of [1] to

[13] , wherein the compound represented by formula (p2) in [II] is a compound represented by formula (p2-1):

[16] The material for forming an X-ray structural analysis sample according to any one of [1] to

[15] , wherein a content ratio of the carboxylic acid-based ligand (c) to the pyridine-based ligand (p) [carboxylic acid-based ligand (c) / pyridine-based ligand (p); molar ratio] is 30 / 70 to 70 / 30.

[17] The X-ray structural analysis sample forming material according to any one of [1] to

[16] , wherein the content ratio of the metal ion to the carboxylic acid-based ligand (c) [metal ion / carboxylic acid-based ligand (c); molar ratio] is 30 / 70 to 70 / 30.

[18] The X-ray structural analysis sample forming material according to any one of [1] to

[17] , wherein the content ratio of the metal ion to the pyridine-based ligand (p) [metal ion / pyridine-based ligand (p); molar ratio] is 30 / 70 to 70 / 30.

[19] The X-ray structural analysis sample forming material according to any one of [1] to

[18] , wherein the total content of the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) accounts for 50 wt % or more of the total amount of ligands constituting the metal complex crystal.

[20] A method for determining the molecular structure of an organic compound (X), comprising the following steps 1 and 2: Step 1: An organic compound (X) is impregnated into the X-ray structural analysis sample formation material according to any one of [1] to

[19] , and the organic compound (X) is fixed in the pores of the X-ray structural analysis sample formation material. Step 2: X-rays are irradiated onto the X-ray structural analysis sample formation material to which the organic compound (X) has been fixed, and the obtained diffraction data is analyzed to determine the molecular structure of the organic compound (X).

[21] A method for determining the molecular structure of a gaseous odorous component (Y), comprising the following steps 1, 2, and 3: Step 1: A sample gas containing the gaseous odor component (Y) is supplied to a gas component separation column, and the gaseous odor component (Y) is separated. Step 2: The separated gaseous odor component (Y) is permeated into the X-ray structural analysis sample formation material described in any one of [1] to

[19] , and the gaseous odor component (Y) is fixed in the pores of the X-ray structural analysis sample formation material. Step 3: The X-ray structural analysis sample formation material to which the gaseous odor component (Y) has been fixed is irradiated with X-rays, and the obtained diffraction data is analyzed to determine the molecular structure of the gaseous odor component (Y).

[22] Use of the following metal complex crystal as a material for forming a sample of an organic compound for X-ray structural analysis. Metal complex crystal: A metal complex crystal composed of a metal ion and a ligand coordinated to the metal ion, wherein the metal complex crystal has a three-dimensional network structure with regularly aligned pores, the ligands include a carboxylic acid-based ligand (c) and a pyridine-based ligand (p), and the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) are a combination of the following [I] or [II]:[I] A compound represented by formula (c1) and a compound represented by formula (p1) [II] A compound represented by formula (c2) and a compound represented by formula (p2)

[23] Use of the organic compound according to

[22] as a material for forming a sample for X-ray structural analysis, wherein the metal ion is selected from zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions.

[24] Use of the organic compound according to

[22] or

[23] as a material for forming a sample for X-ray structural analysis, wherein the organic compound is an organic compound having a functional group that interacts with at least one group selected from CONH groups, CO groups, and NH groups.

[25] Use of the organic compound according to

[22] or

[23] as a material for forming a sample for X-ray structural analysis, wherein the organic compound is an organic compound having at least one functional group selected from substituted or unsubstituted amino groups, carboxyl groups, active methylene groups, nitrile groups, ketone groups, aldehyde groups, ester groups, ether groups, amide groups, hydroxy groups, halogen groups, and sulfonamide groups.

[26] Use of the organic compound according to any one of

[22] to

[25] as a material for forming a sample for X-ray structural analysis, wherein the organic compound has a log P value of -5 to 7.

[27] Use of the organic compound according to any one of

[22] to

[26] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (c1) in [I] is at least one compound selected from the compounds represented by formulas (c1-1) to (c1-4).

[28] Use of the organic compound according to any one of

[22] to

[26] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (c1) in [I] is the compound represented by formula (c1-1).

[29] Use of the organic compound according to any one of

[22] to

[28] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (p1) in [I] is at least one compound selected from the compounds represented by formulas (p1-1) to (p1-7).

[30] Use of the organic compound according to any one of

[22] to

[28] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (p1) in [I] is at least one compound selected from the group consisting of compounds represented by formula (p1-1), formula (p1-2), formula (p1-5), and formula (p1-6).

[31] Use of the organic compound according to any one of

[22] to

[28] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (p1) in [I] is a compound represented by formula (p1-1) and / or a compound represented by formula (p1-2).

[32] Use of the organic compound according to any one of

[22] to

[31] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (c2) in [II] is at least one compound selected from the compounds represented by formulas (c2-1) to (c2-5).

[33] Use of the organic compound according to any one of

[22] to

[31] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (c2) in [II] is a compound represented by formula (c2-1) and / or a compound represented by formula (c2-2).

[34] Use of the organic compound according to any one of

[22] to

[31] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (c2) in [II] is a compound represented by formula (c2-1).

[35] Use of the organic compound according to any one of

[22] to

[34] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (p2) in [II] is at least one compound selected from the compounds represented by formulas (p2-1) to (p2-4).

[36] Use of the organic compound according to any one of

[22] to

[34] as a material for forming a sample for X-ray structural analysis, wherein the compound represented by formula (p2) in [II] is a compound represented by formula (p2-1).

[37] Use of the organic compound according to any one of

[22] to

[36] as a material for forming a sample for X-ray structural analysis, wherein the content ratio of the carboxylic acid ligand (c) to the pyridine ligand (p) [carboxylic acid ligand (c) / pyridine ligand (p); molar ratio] is 30 / 70 to 70 / 30.

[38] Use of the organic compound according to any one of

[22] to

[37] as a material for forming a sample for X-ray structural analysis, wherein the content ratio of the metal ion to the carboxylic acid ligand (c) [metal ion / carboxylic acid ligand (c); molar ratio] is 30 / 70 to 70 / 30.

[39] Use of the organic compound according to any one of

[22] to

[38] as a material for forming a sample for X-ray structural analysis, wherein the content ratio of the metal ion to the pyridine-based ligand (p) [metal ion / pyridine-based ligand (p); molar ratio] is 30 / 70 to 70 / 30.

[40] Use of the organic compound according to any one of

[22] to

[39] as a material for forming a sample for X-ray structural analysis, wherein the total content of the carboxylic acid-based ligand (c) and the pyridine-based ligand (p) accounts for 50 wt % or more of the total amount of ligands constituting the metal complex crystal.

[0142] By using the material for forming an X-ray structural analysis sample according to the present disclosure, even when the amount of organic compound (X) is too small to form a single crystal, or even when the organic compound (X) is a compound that cannot be formed into a single crystal, or even when the organic compound (X) is in a solid, liquid, or gaseous state, it is possible to determine the molecular structure by X-ray structural analysis.

[0143] REFERENCE SIGNS LIST 1 Gas chromatograph fractionator 2 Inlet 3 Column 4 Branching section 5 Detector 6 Column heating tank 7 Fractionation tube 8 Discharge line 9 Fractionation tube cooling tank 10 Carrier gas

Claims

1. A material for forming an X-ray structural analysis sample containing an organic compound in a regularly aligned state, the material comprising the following metal complex crystal: Metal complex crystal: A metal complex crystal composed of a metal ion and a ligand coordinated to the metal ion, the metal complex crystal having a three-dimensional network structure with regularly aligned pores, the ligand including a carboxylic acid ligand (c) and a pyridine ligand (p), the carboxylic acid ligand (c) and the pyridine ligand (p) being a combination of the following [I] or [II]: [I] A compound represented by the following formula (c1) and a compound represented by the following formula (p1): [II] A compound represented by the following formula (c2) and a compound represented by the following formula (p2): (In the formula, R １ , R ２ L may be the same or different and represents a group selected from a single bond, a divalent hydrocarbon group, a divalent heterocyclic group, and a divalent group formed by linking two or more of the above groups. １ ~L ４ are the same or different and represent a single bond or a linking group.

2. The material for forming an X-ray structural analysis specimen according to claim 1, wherein the metal ion is selected from the group consisting of zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions.

3. The material for forming an X-ray structural analysis sample according to claim 1 or 2, wherein the organic compound is an organic compound having a functional group that interacts with at least one group selected from the group consisting of a CONH group, a CO group, and an NH group.

4. The X-ray structural analysis sample forming material according to claim 1 or 2, wherein the organic compound is an organic compound having at least one functional group selected from a substituted or unsubstituted amino group, a carboxyl group, an active methylene group, a nitrile group, a ketone group, an aldehyde group, an ester group, an ether group, an amide group, a hydroxyl group, a halogen group, and a sulfonamide group.

5. The material for forming an X-ray structural analysis specimen according to claim 1 or 2, wherein the organic compound has a log P value of -5 or more and 7 or less.

6. A method for determining the molecular structure of an organic compound (X), comprising the following steps 1 and 2. Step 1: Permeating the material for forming a specimen for X-ray structural analysis according to claim 1 or 2 with the organic compound (X) to fix the organic compound (X) in the pores of the material for forming a specimen for X-ray structural analysis. Step 2: Irradiating the material for forming a specimen for X-ray structural analysis with the organic compound (X) fixed thereto with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the organic compound (X).

7. A method for determining the molecular structure of a gaseous odorous component (Y), comprising the following steps 1, 2, and 3: Step 1: Supplying a sample gas containing the gaseous odor component (Y) to a gas component separation column to separate the gaseous odor component (Y). Step 2: Permeating the separated gaseous odor component (Y) into the X-ray structure analysis sample formation material according to claim 1 or 2 to fix the gaseous odor component (Y) in the pores of the X-ray structure analysis sample formation material. Step 3: Irradiating the X-ray structure analysis sample formation material to which the gaseous odor component (Y) has been fixed with X-rays, and analyzing the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

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