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

Abstract

This invention provides a novel material for preparing X-ray structural analysis samples of organic compounds. The X-ray structural analysis sample forming material of this disclosure comprises a metal complex crystal. The metal complex crystal comprises a metal ion and a ligand coordinated to the metal ion, the metal complex crystal having a three-dimensional network structure with regularly ordered pores, the ligand comprising 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 formula (c1) and a compound represented by formula (p1); [II] a compound represented by formula (c2) and a compound represented by formula (p2).

Description

Technical Field

[0001] This disclosure relates to novel X-ray structure analysis sample forming materials and methods for determining the molecular structure of organic compounds using the aforementioned X-ray structure analysis sample forming materials. This disclosure claims priority to Japanese Patent Application No. 2023-202754, filed on November 30, 2023, the contents of which are incorporated herein by reference. Background Technology

[0002] One known method for determining the molecular structure of organic compounds is single-crystal X-ray structure analysis, which involves analyzing the structure of a single crystal of an organic compound using X-rays. This method is particularly useful if high-quality single crystals can be produced, allowing for accurate determination of the molecular structure of organic compounds.

[0003] However, when organic compounds are present in trace amounts, it is impossible to obtain a sufficient quantity of single crystals, making it difficult to determine the molecular structure using the methods described above. Furthermore, there are organic compounds that are difficult to crystallize, and for such compounds, the methods described above cannot be used.

[0004] To this end, a crystal sponge method has been developed, which allows for the determination of the molecular structure of organic compounds via X-ray structural analysis without the need for crystallization (e.g., Patent Document 1). The crystal sponge method involves using a metal complex crystal with regularly ordered pores as an X-ray structural analysis sample forming material (or a crystal sponge), and impregnating the organic compound whose molecular structure is to be determined, along with a solvent, within the pores of the metal complex crystal. The material, which arranges the organic compound in a regularly ordered manner, serves as the X-ray structural analysis sample (i.e., the sample for X-ray structural analysis). The resulting X-ray structural analysis sample is irradiated with X-rays to determine the molecular structure of the organic compound.

[0005] Furthermore, Non-Patent Document 1 discloses that a metal complex crystal with regularly ordered pores can be obtained by reacting 1,3-bis(4-pyridylaminocarbonyl)benzene, 4,4'-biphenyldicarboxylic acid, and zinc nitrate hydrate. However, it does not disclose the use of the aforementioned metal complex crystal as a sample forming material for X-ray structural analysis.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2014 / 038220

[0009] Non-patent literature

[0010] Non-patent document 1: Optimization of Reaction Conditions towards MultipleTypes of Framework Isomers and Periodic-Increased Porosity: LuminescenceProperties and Selective CO2 Adsorption over N2, ChemPhysChem, 2013, 14, 3594-3599. Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] When the metal complex crystal described in Patent Document 1 is used as the sample forming material for X-ray structural analysis, the probability of determining the molecular structure of organic compounds is about 30%, which is a problem of low success rate.

[0013] In addition, by optimizing the type of solvent and impregnation temperature used when impregnating the organic compound with the metal complex crystal according to the type of organic compound, the success rate of molecular structure determination can be improved. However, the metal complex crystal described in Patent Document 1 has poor solvent resistance and will dissolve in medium to high polarity solvents, so there is a problem that there are few types of solvents that can be used.

[0014] Furthermore, since the metal complex crystal described in Patent Document 1 has a hydrophobic environment inside its pores, it is difficult to retain hydrophilic organic compounds inside the pores of the metal complex crystal, and it is difficult to use the metal complex crystal to determine the molecular structure of hydrophilic organic compounds.

[0015] Furthermore, the metal complex crystal described in Patent Document 1 cannot maintain its crystal structure unless the pores are filled with solvent. Therefore, for the aforementioned metal complex crystal, it is not possible to use a method that fills the pores with a gas containing a gaseous organic compound to fix the gaseous organic compound within the pores.

[0016] Therefore, the purpose of this disclosure is to provide a novel material for preparing X-ray structural analysis samples of organic compounds, which enables the organic compounds to be arranged and fixed in a regular and orderly manner.

[0017] Another object of this disclosure is to provide a novel material for preparing X-ray structural analysis samples of organic compounds, which enables hydrophilic organic compounds to be arranged and fixed in a regular and orderly manner.

[0018] Another object of this disclosure is to provide a novel material for preparing X-ray structural analysis samples of organic compounds, which enables the gaseous organic compounds present in a gas to be arranged in a regular and orderly manner and fixed.

[0019] Another objective of this disclosure is to provide a method for determining the molecular structure of organic compounds using the aforementioned materials.

[0020] Another objective of this disclosure is to provide a method for determining the molecular structure of odor components using the aforementioned materials.

[0021] Problem Solving Methods

[0022] In order to solve the above problems, the inventors conducted in-depth research and discovered the following:

[0023] In other words, to determine the molecular structure of an organic compound, it is necessary to arrange the organic compound in a regular and orderly manner. However, regarding the metal complex crystal described in Patent Document 1, since the organic compound is immobilized within the pores through relatively weak intermolecular interactions such as π-π and σ-π interactions, the probability of it remaining within the pores is low. Furthermore, regarding the metal complex crystal described in Patent Document 1, it is known that due to its weak ability to arrange the organic compound in a regular and orderly manner, the probability of determining the molecular structure is low when using the aforementioned metal complex crystal as a crystal sponge.

[0024] On the other hand, it was discovered that amide groups can interact strongly with various functional groups through hydrogen bonds. If a specific ligand with an amide group is coordinated with a metal ion, a metal complex crystal with regularly ordered pores can be obtained. This type of metal complex crystal can contain organic compounds within the regularly ordered pores with a high probability, and the contained organic compounds are firmly maintained in an oriented state. Therefore, if the aforementioned metal complex crystal is used as a sample forming material for X-ray structural analysis, the molecular structure of the organic compound can be determined with a high probability by X-ray diffraction. This disclosure is based on these insights.

[0025] That is, this disclosure provides an X-ray structure analysis sample forming material, which is a forming material for forming X-ray structure analysis samples containing organic compounds in a regular and ordered arrangement, the forming material comprising the following metal complex crystals.

[0026] Metal complex crystal: a metal complex crystal comprising a metal ion and a ligand coordinated to the metal ion, the metal complex crystal having a three-dimensional network structure with regularly ordered pores, the ligand comprising 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].

[0027] [I] The compound represented by formula (c1) below and the compound represented by formula (p1) below.

[0028] [II] The compound represented by formula (c2) below and the compound represented by formula (p2) below.

[0029] [Chemical Formula 1]

[0030]

[0031] (where R is in the formula) 1 R 2 "Same" or "different" refers to groups selected from single bonds, divalent hydrocarbon groups, divalent heterocyclic groups, and divalent groups formed by the linkage of two or more of the above groups. L 1 ~L 4 (This indicates the presence or absence of identical or different single bonds or linking groups.)

[0032] This disclosure also provides the sample forming material for the above-mentioned X-ray structural analysis, wherein the metal ions are selected from zinc ions, iron ions, cobalt ions, nickel ions, copper ions and silver ions.

[0033] This disclosure also provides the above-mentioned X-ray structural analysis sample forming material, wherein the above-mentioned organic compound has a functional group that interacts with at least one group selected from CONH group, CO group and NH group.

[0034] This disclosure also provides the above-mentioned X-ray structural analysis sample forming material, wherein the above-mentioned organic compound has at least one functional group selected from substituted or unsubstituted amino, carboxyl, active methylene, nitrile, ketone, aldehyde, ester, ether, amide, hydroxyl, halogen, and sulfonamide.

[0035] This disclosure also provides the above-mentioned X-ray structural analysis sample forming material, wherein the organic compound is an organic compound with a logP value of -5 or higher and 7 or lower.

[0036] This disclosure also provides a method for determining the molecular structure of an organic compound (X), which includes the following steps 1 and 2.

[0037] Step 1: The organic compound (X) is impregnated into the X-ray structure analysis sample forming material to fix the organic compound (X) in the pores of the X-ray structure analysis sample forming material;

[0038] Step 2: Irradiate the X-ray structure analysis sample formed by fixing the organic compound (X) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the organic compound (X).

[0039] This disclosure also provides a method for determining the molecular structure of a gaseous odor component (Y), which includes the following steps 1, 2, and 3.

[0040] Step 1: Feed a sample gas containing gaseous odor component (Y) into a column for gas component separation, and separate and collect the gaseous odor component (Y);

[0041] Step 2: The gaseous odor component (Y) collected by separation is impregnated into the X-ray structure analysis sample forming material to fix the gaseous odor component (Y) in the pores of the X-ray structure analysis sample forming material;

[0042] Step 3: Irradiate the X-ray structure analysis sample material after fixing the gaseous odor component (Y) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0043] The effects of the invention

[0044] The X-ray structural analysis specimens disclosed herein comprise metallic complex crystals with large, regularly ordered pores.

[0045] Furthermore, the shape of the pores in the aforementioned metal complex crystal is not fixed, exhibiting variability that allows it to deform according to the shape of the introduced organic compound (the so-called guest molecule). Therefore, various organic compounds can be introduced into the pores of the aforementioned metal complex crystal with a high probability.

[0046] Furthermore, the aforementioned metal complex crystal possesses amide groups, which are groups capable of forming hydrogen bonds with various functional groups. Therefore, organic compounds introduced into the pores of the aforementioned metal complex crystal can be fixed in a highly probable and robustly ordered arrangement.

[0047] Furthermore, since the aforementioned metal complex crystals have amide groups, their pores create a hydrophilic environment, which can introduce hydrophilic organic compounds into the pores with a high probability and fix them in place.

[0048] In addition, the above-mentioned metal complex crystals have excellent solvent resistance and can maintain their crystal structure in various solvents.

[0049] In addition, the above-mentioned metal complex crystals have excellent strength and toughness, and can maintain their crystal structure regardless of whether the pores are filled with solvent or not (i.e., filled with air).

[0050] Therefore, it is possible not only to impregnate (or to impregnate) liquid organic compounds (X) (or to impregnate a material formed by dissolving solid organic compounds (X) in a solvent) and fix them in the pores of the X-ray structure analysis sample forming material, but also to impregnate and fix gaseous organic compounds (X) in the pores of the X-ray structure analysis sample forming material.

[0051] Therefore, if the above-mentioned X-ray structural analysis of the sample forming material is used, it is possible to fix solid, liquid or gaseous organic compounds (X) in the pores with a high probability, and to arrange the above-mentioned organic compounds (X) in a regular and orderly manner in the metal complex crystal.

[0052] If the above-mentioned X-ray structure analysis sample forming material is used, even if the organic compound (X) is too small for single crystallization or is a compound that cannot be single crystallized, it can be arranged regularly and orderly in the pores of the X-ray structure analysis sample forming material, so that the molecular structure of the organic compound (X) can be determined by performing X-ray structure analysis on the X-ray structure analysis sample obtained in this way.

[0053] Therefore, the X-ray structure analysis of the sample forming material described above is an extremely useful means of determining the molecular structure of organic compounds (X) (especially hydrophilic organic compounds) based on X-ray structure analysis, whether the sample is a solid, liquid, or gas. Attached Figure Description

[0054] Figure 1 This is a schematic diagram showing the crystal structure of the sample forming material 1 obtained in the embodiment.

[0055] Figure 2 This is a schematic diagram showing the crystal structure of material 4 formed by the sample obtained in the comparative example.

[0056] Figure 3 The schematic diagram of the crystal structure of the X-ray structure analysis sample (a metal complex crystal with benzoyl immobilized in the pores) obtained in Example 14 is shown below. Figure 3 (a); A schematic diagram showing the shape of the pores in the X-ray structure analysis sample is shown below. Figure 3 (b); The state in which the NH group constituting the amide group of sample forming material 1 interacts with the oxygen atom of the oxo group of benzoyl is shown in the figure. Figure 3 (c)

[0057] Figure 4In the figure, a schematic diagram of the crystal structure of the X-ray structure analysis sample (a metal complex crystal with dibutyl fumarate fixed in the pores) obtained in Example 22 is shown. Figure 4 (a); A schematic diagram showing the shape of the pores in the X-ray structure analysis sample is shown below. Figure 4 (b); The interaction between the NH group constituting the amide group of sample forming material 1 and the oxygen atom of the oxy group of dibutyl fumarate is shown in the figure. Figure 4 (c)

[0058] Figure 5 This is a schematic diagram of the analytical apparatus used in determining the structure of odor components in the embodiment. The analytical apparatus has a splitter mounted directly in front of the detector of the gas chromatograph and is connected to a separation and collection device.

[0059] Symbol Explanation

[0060] 1 Gas Chromatography Separation and Collection Apparatus

[0061] 2. Inlet

[0062] 3. Chromatographic column

[0063] 4. Flow branch

[0064] 5 detectors

[0065] 6. Column heating bath

[0066] 7. Separation and collection tube

[0067] 8. Discharge pipeline

[0068] 9. Separation and collection pipe cooling tank

[0069] 10 carrier gas Detailed Implementation

[0070] [X-ray structural analysis of sample forming materials]

[0071] The X-ray structure analysis specimen forming material disclosed herein (hereinafter sometimes referred to as "specimen forming material") is a material sometimes called a crystal sponge for forming specimens for X-ray structure analysis, and is a material that can be used to fix organic compounds in a regular and orderly arranged state.

[0072] The sample forming material described above contains at least the following metal complex crystals. The sample forming material may also contain other components, but the proportion of the following metal complex crystals 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, 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 substantially consist only of the following metal complex crystals.

[0073] (Metal complex crystal)

[0074] Metal complex crystals are metal complex crystals (preferably fine-porous metal complex crystals) that are composed of metal ions and ligands coordinated with the metal ions and have a three-dimensional network structure with regularly and orderly arranged pores.

[0075] The aforementioned metal ions are not particularly limited to any metal ion that enables the ligands described later to form a three-dimensional network structure through coordination bonding. Examples include ions of metals from groups 8 to 12 of the periodic table, such as zinc, iron, cobalt, nickel, copper, and silver. From the viewpoint of obtaining a metal complex crystal with a large porosity three-dimensional network structure, divalent metal ions are preferred, and zinc and / or cobalt ions are particularly preferred.

[0076] The aforementioned ligands include at least one carboxylic acid ligand (c) and at least one pyridine ligand (p).

[0077] The combination of the above-mentioned carboxylic acid ligand (c) and pyridine ligand (p) is as follows [I] or [II].

[0078] [I] The compound represented by formula (c1) below and the compound represented by formula (p1) below.

[0079] [II] The compound represented by formula (c2) below and the compound represented by formula (p2) below.

[0080] [Chemical Formula 2]

[0081]

[0082] (where R is in the formula) 1 R 2 "Same" or "different" refers to a group selected from single bonds, divalent hydrocarbon groups, divalent heterocyclic groups, and divalent groups formed by the linkage of two or more of the above groups. L 1 ~L 4 (Identical or different, indicating single bonds or linking groups)

[0083] As R 1R 2 The divalent hydrocarbon group in the name can be exemplified by: alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene, which are straight-chain or branched alkylene groups with 1 to 18 carbon atoms; cycloalkylene groups such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylene; phenylene (e.g., ortho-phenylene, meta-phenylene, para-phenylene), phenylene bis(methylene) (e.g., 1,2-phenylene bis(methylene), 1,3-phenylene bis(methylene), 1,4-phenylene bis(methylene)), biphenylene, naphthylene, binatylene, anthraceneylene, and phenanthrene, etc. 6-14 Alpha-aryl, etc.

[0084] R 1 R 2 The divalent heterocyclic group is a group formed by removing two hydrogen atoms from the structural formula of a heterocycle. The aforementioned heterocycles include aromatic heterocycles and non-aromatic heterocycles. Examples of such heterocycles include 3- to 20-membered rings (preferably 3- to 10-membered rings, particularly 4- to 6-membered rings) and their fused rings, in which the atoms constituting the ring have carbon atoms and at least one heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.).

[0085] Examples of heterocycles containing oxygen atoms as heteroatoms include: 3-membered rings such as ethylene oxide rings; 4-membered rings such as oxo-butane rings; furan rings, tetrahydrofuran rings, etc. azole ring, iso- Five-membered rings such as azole rings and γ-butyrolactone rings; six-membered rings such as 4-oxo-4H-pyran rings, tetrahydropyran rings, and morpholine rings; fused rings such as benzofuran rings, isobenzofuran rings, 4-oxo-4H-chromene rings, chromene rings, and isochorene rings; 3-oxatricyclic rings [4.3.1.1] 4,8 Undecane-2-one ring, 3-oxatricycle [4.2.1.0] 4,8 Nonane-2-one ring and other bridged rings, etc.

[0086] Examples of heterocycles containing sulfur atoms as heteroatoms include: 5-membered rings such as thiophene rings, thiazole rings, isothiazole rings, and thiadiazole rings; 6-membered rings such as 4-oxo-4H-thiopyran rings; and fused rings such as benzothiophene rings.

[0087] Examples of heterocycles containing nitrogen atoms as heteroatoms include: 5-membered rings such as pyrrole rings, pyrrolidine rings, pyrazole rings, imidazole rings, and triazole rings; 6-membered rings such as isocyanuric acid rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, and piperazine rings; and fused rings such as indole rings, dihydroindole rings, quinoline rings, acridine rings, naphthidine rings, quinazoline rings, and purine rings.

[0088] L1 ~L 4 The terms "same" or "different" indicate single bonds or linking groups. The linking groups mentioned above are divalent groups with one or more atoms, such as divalent hydrocarbon groups.

[0089] Examples of divalent hydrocarbon groups mentioned above include: alkylene groups with 1 to 18 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene, which are straight-chain or branched; alkylene groups with 3 to 18 carbon atoms, such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylene; and phenylene groups (e.g., ortho-phenylene, meta-phenylene, and para-phenylene), naphthylene groups (e.g., 1,3-naphthylene, 1,4-naphthylene, and 2,7-naphthylene), anthracene, and phenanthrene groups. 6-14 arylene groups; and groups consisting of two or more of them linked together [e.g., phenylbis(methylene) (e.g., 1,2-phenylbis(methylene), 1,3-phenylbis(methylene), 1,4-phenylbis(methylene)), biphenyl, binatyl] etc.

[0090] As the aforementioned divalent hydrocarbon group, C is preferred. 6-14 arylene, two or more of the above-mentioned arylene groups via a single bond or C 1-5 A group formed by alkylene bonding.

[0091] In addition to the groups shown in the formulas (c1)(p1)(c2)(p2), the benzene ring and pyridine ring in the above formulas may also have substituents.

[0092] Examples of substituents mentioned above include: halogen atoms, oxo groups, hydroxyl groups, and substituted oxygen groups (e.g., C10, C20, C30, C40, C50, C6 ... 1-4 alkoxy), cyano, nitro, substituted or unsubstituted amino groups (e.g., methylamino, dimethylamino, ethylamino, diethylamino, etc., mono- or di-C). 1-4 Alkylamino groups; 5- to 8-membered cyclic amino groups such as 1-pyrrolidinyl, piperidinyl, and morpholinyl; acetamido, propionylamino, benzoylamino, etc. 1-10 Acylamino; sulfonylamino, p-toluenesulfonylamino, etc.), sulfonic acid group, alkyl group (e.g., methyl, ethyl, etc. C 1-4 Alkyl), alkenyl (e.g., vinyl, allyl, 1-butenyl, etc. C 2-4 alkenyl), alkynyl (e.g., ethynyl, propynyl, etc. C 2-4 alkynyl group), C 3-8 Cycloalkyl, aryl (e.g., phenyl, naphthyl, etc. C 6-10 Aryl groups, etc.

[0093] When the benzene ring or pyridine ring in the above formulas (c1)(p1)(c2)(p2) has two or more substituents, two groups selected from the above substituents can also bond with each other to form a ring.

[0094] Furthermore, aromatic or non-aromatic hydrocarbon rings or heterocycles may also be fused onto the benzene ring, pyridine ring, in the above formulas (c1)(p1)(c2)(p2).

[0095] Specific examples of compounds represented by formula (c1) above can be given by compounds represented by formulas (c1-1) to (c1-4) below. In the compounds represented by formula (c1-1) below, the bonding position relative to the carboxyl group of the benzene ring is included, and the relationship between CONH-L in formula (c1) above is... 1 Base and CONH-L 2 Compounds in which the corresponding CONH group is bonded to the ortho, meta, or para position. The same applies to compounds represented by the following formulas (c1-2) to (c1-4).

[0096] [Chemical Formula 3]

[0097]

[0098] From the viewpoint that a metal complex crystal with a three-dimensional network structure having large pores can be obtained by using the compound represented by the above formula (c1), the compound represented by the above formula (c1-1) is preferred.

[0099] As a specific example of the compound represented by the above formula (p1), examples can be given of compounds represented by the following formulas (p1-1) to (p1-7) where R in formula (p1) is related to R. 1 The corresponding group is bonded to the nitrogen atom of the pyridine ring in the para-position of the compound, and the compound corresponding to the above compound has R in formula (p1). 1 Compounds in which the corresponding group is bonded to the nitrogen atom of the pyridine ring at the ortho or meta position.

[0100] [Chemical Formula 4]

[0101]

[0102] From the viewpoint that a metal complex crystal with a three-dimensional network structure having large pores can be obtained as the compound represented by the above formula (p1), the compounds represented by the above formula (p1-1), the above formula (p1-2), the above formula (p1-5), and the above formula (p1-6) are preferred, and the compounds represented by the above formula (p1-1) and the compounds represented by the above formula (p1-2) are particularly preferred.

[0103] Specific examples of compounds represented by formula (c2) above can be given by compounds represented by formulas (c2-1) to (c2-5) below. Among the compounds represented by formula (c2-1) below, there are compounds in which the carboxyl group is bonded to the ortho, meta, or para position relative to the linking site of the benzene ring. The same applies to the compounds represented by formulas (c2-2) to (c2-5) below.

[0104] [Chemical Formula 5]

[0105]

[0106] In the above formula (c2-2), L represents a linking group. The linking group is a divalent group with one or more atoms, such as carbonyl (-CO-), ether (-O-), thioether (-S-), ester (-COO-), amide (-CONH-), imine (-NH-), sulfonyl (-S(=O)2-), etc.

[0107] From the viewpoint that a metal complex crystal with a three-dimensional network structure having large pores can be obtained by using the compound represented by formula (c2) above, the compound represented by formula (c2-1) and the compound represented by formula (c2-2) above are preferred, and the compound represented by formula (c2-1) above is particularly preferred.

[0108] Specific examples of compounds represented by formula (p2) above can be given by compounds represented by formulas (p2-1) to (p2-4) below. Among the compounds represented by formula (p2-1) below, those containing the compounds with CONH-L from formula (p2) above are included. 3 Base and CONH-L 4 Compounds in which the corresponding group is bonded to the nitrogen atom of the pyridine ring at the ortho, meta, or para position. The same applies to compounds represented by the following formulas (p2-2) to (p2-4).

[0109] [Chemical Formula 6]

[0110]

[0111] From the viewpoint that a metal complex crystal with a three-dimensional network structure having large pores can be obtained by using the compound represented by the above formula (p2), the compound represented by the above formula (p2-1) is preferred.

[0112] The ligands constituting the above-mentioned metal complex crystals include carboxylic acid ligands (c) and pyridine ligands (p). From the viewpoint that a molar ratio of carboxylic acid ligands (c) to pyridine ligands (p) [carboxylic acid ligands (c) / pyridine ligands (p); molar ratio] of 30 / 70 to 70 / 30 can yield metal complex crystals with a three-dimensional network structure and large porosity, it is preferred to be 40 / 60 to 60 / 40, and particularly preferred to be 45 / 55 to 55 / 45.

[0113] The ratio of metal ions to carboxylic acid ligands (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.

[0114] The content ratio of metal ions to pyridine ligands (p) [metal ion / pyridine 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.

[0115] In addition to carboxylic acid ligands (c) and pyridine ligands (p), the above ligands may also include other ligands. Examples of other ligands include: F - Cl - ,Br - I - SCN - NO3 - ClO4 - BF4 - SbF4 - PF6 - AsF6 - CH3COO - Anions.

[0116] From the viewpoint that a metal complex crystal with a large porous three-dimensional network structure can be obtained by using the above-mentioned anion, it is preferable to select NO3. - F - Cl - ,Br - and I - The anions in it are particularly preferred to be NO3. - .

[0117] In the total amount of ligands constituting the above-mentioned metal complex crystal, the proportion of the combined content of the above-mentioned carboxylic acid ligands (c) and pyridine ligands (p) is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

[0118] The aforementioned metal complex crystal possesses a three-dimensional network structure with regularly ordered pores. These pores are spaces existing within the aforementioned metal complex crystal, separated by a network structure composed of metal ions and ligands.

[0119] The aforementioned pores are preferably not disordered to the extent that they can be confirmed by X-ray structural analysis, and are arranged in a regular and orderly manner in three dimensions.

[0120] There are no particular restrictions on the shape of the pores, but each pore is preferably of a certain shape and size that can be confirmed by X-ray structural analysis.

[0121] The shape of the aforementioned pores is variable, changing according to the shape of the organic compound (X) introduced into the pores. This is because the aforementioned metal complex crystal is not composed of a series of three-dimensional network structures, but rather of multiple (e.g., three or more, preferably four or more) independent three-dimensional network structures interpenetrating each other.

[0122] As for the size of the pores present within a unit cell, it is preferable to have a volume that is capable of encapsulating one to several (e.g., one to six) organic compounds (X).

[0123] The size of the pore is related to the diameter of the inscribed circle, which is the inscribed circle of the pore within a plane (hereinafter sometimes referred to as the parallel plane) that is closest to the perpendicular crystal plane relative to the direction in which the pore extends. The larger the inscribed circle, the larger the pore; the smaller the inscribed circle, the smaller the pore.

[0124] The "direction of pore extension" mentioned above can be determined by the following method.

[0125] First, a crystal plane 1 (one of the six crystal planes connecting the four lattice points contained in a unit cell) is selected in an appropriate direction traversing the pores of the object. Next, the atoms constituting the aforementioned metal complex crystal and existing on crystal plane 1 are represented using van der Waals radii, thereby depicting a cross-sectional view of the pores with crystal plane 1 as the cut surface. Similarly, a cross-sectional view of the pores with crystal plane 2, which is offset from crystal plane 1 by one unit cell, is depicted. Then, in a three-dimensional view, the centers of the cross-sectional shapes of the pores in each crystal plane are connected by straight lines. The direction of the resulting straight lines is the direction of pore extension.

[0126] In addition, the diameter of the inscribed circle of the pore can be determined by the following method.

[0127] First, a cross-sectional view of the pore is drawn using the method described above. Next, the inscribed circle is drawn in this cross-sectional view, and its diameter is measured. The measured value is then converted into actual dimensions, from which the actual diameter of the inscribed circle of the pore can be determined.

[0128] Furthermore, while slowly moving the aforementioned parallel planes parallel within a unit cell, a cross-sectional view of the pores within each parallel plane is drawn and the diameter of its inscribed circle is measured. From this, the diameter of the inscribed circle of the narrowest part and the diameter of the inscribed circle of the widest part can be determined.

[0129] The diameter of the inscribed circle of the pore is, for example, 8 to 12 Å, preferably 9 to 12 Å.

[0130] In addition, when the shape of the pore differs significantly from that of a perfect circle, it is preferable to predict the size of the pore based on the minor and major axes of the inscribed ellipse of the pore in the aforementioned parallel plane.

[0131] The major axis of the inscribed ellipse of the pore is preferably 10~15 Å, more preferably 10~12 Å. Furthermore, the minor axis of the inscribed ellipse of the pore is preferably 8~15 Å, more preferably 8~11 Å.

[0132] The aforementioned metal complex crystal contains ligands with amide groups (CONH) as constituent elements. The amide groups (CONH groups), the CO groups constituting the amide groups, and the NH groups can interact with various functional groups via hydrogen bonds. Therefore, the aforementioned metal complex crystal can determine the molecular structures of a wide range of organic compounds, or a large variety of organic compounds. Furthermore, the aforementioned metal complex crystal can firmly fix organic compounds within its pores through hydrogen bonds with the amide, CO, or NH groups. Therefore, by using the aforementioned metal complex crystal, the molecular structures of various organic compounds having functional groups that interact with amide, CO, or NH groups can be determined with a high probability.

[0133] Furthermore, the aforementioned metal complex crystals exhibit excellent durability, maintaining their crystal structure not only in solution but also in air. Therefore, even volatile organic compounds that vaporize and disperse in the gas phase can be introduced and immobilized within the pores of the aforementioned metal complex crystals. Thus, these metal complex crystals can also be used to impregnate and immobilize odor components in a gaseous state, thereby determining their molecular structure, demonstrating excellent versatility.

[0134] [Preparation Method of X-ray Structural Analysis Sample Formation Material]

[0135] The sample forming material for the above X-ray structural analysis can be manufactured using the following method for manufacturing metal complex crystals.

[0136] (Method for manufacturing metal complex crystals)

[0137] Metal complex crystals can be produced, for example, by reacting carboxylic acid ligands (c), pyridine ligands (p), and salts of metal ions and counterions (hereinafter sometimes referred to as "metal salts") in the presence of a solvent.

[0138] Examples of counterions to the above-mentioned ions include: F - Cl - ,Br - I - SCN - NO3 - ClO4 - BF4 - SbF4 - PF6 - AsF6 - CH3COO - Anions.

[0139] The ratio of carboxylic acid ligand (c) to pyridine ligand (p) [carboxylic acid ligand (c) / pyridine ligand (p); molar ratio] is, for example, 30 / 70 to 70 / 30. From the viewpoint that a metal complex crystal with a three-dimensional network structure with large pores can be obtained, the above-mentioned ratio is preferably 40 / 60 to 60 / 40, and particularly preferably 45 / 55 to 55 / 45.

[0140] The amount of metal salt used relative to 1 mole of carboxylic acid ligand (c) or pyridine ligand (p) is, for example, 0.2 to 3 moles, preferably 0.5 to 2 moles, and particularly preferably 0.8 to 1.5 moles.

[0141] Examples of solvents mentioned above include: water; benzene; benzene derivatives such as toluene, xylene, ethylbenzene, trifluoromethylbenzene (or trifluorotoluene), chlorobenzene, anisole, benzonitrile, nitrobenzene, and ethyl benzoate, in which at least one of the hydrogen atoms bonded to the benzene ring is replaced by a halogen atom, alkyl group, haloalkyl group, alkoxy group, cyano group, nitro group, or substituted oxycarbonyl group; 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; and diethyl ether, dibutyl ether, dimethoxyethane, and diethyl ether. Alkane, tetrahydrofuran, and other chain or cyclic ethers; acetic acid and other organic acids. These can be used alone or in combination of two or more.

[0142] As the solvent mentioned above, a mixture of water and amide (especially DMF) is preferred. The volume ratio of water relative to the total volume of water and amide is, for example, 5 to 95 vol%. From the viewpoint that a metal complex crystal with a three-dimensional network structure with large pores can be obtained, the lower limit of the above volume ratio is preferably 10 vol%, particularly preferably 15 vol%, and the upper limit is preferably 80 vol%, particularly preferably 60 vol%, more preferably 50 vol%, further preferably 40 vol%, particularly preferably 30 vol%, most preferably 25 vol%, and especially preferably 17 vol%.

[0143] The temperature of the above reaction is, for example, 60~150℃, preferably 80~120℃, and particularly preferably 90~110℃.

[0144] 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.

[0145] The reaction atmosphere is not particularly limited as long as it does not hinder the reaction; for example, it can be any gas atmosphere such as air, nitrogen, or argon.

[0146] After the reaction is complete, the reaction product can be separated and purified by precipitation, washing, or filtration.

[0147] [Methods for determining the molecular structure of organic compound (X)]

[0148] The method for determining the molecular structure of the above-mentioned organic compound (X) includes the following steps 1 and 2.

[0149] Step 1: The organic compound (X) is impregnated into the above-mentioned sample forming material (or, the above-mentioned metal complex crystal) to fix the organic compound (X) in the pores of the above-mentioned sample forming material (or, the above-mentioned metal complex crystal).

[0150] Step 2: Irradiate the sample forming material (or the metal complex crystal) after fixing the organic compound (X) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the organic compound (X).

[0151] The organic compound (X) is, for example, a compound having at least one functional group that interacts with the amide group (CONH group), CO group or NH group constituting the amide group via hydrogen bonding with the sample forming material (or the metal complex crystal) described above.

[0152] Examples of functional groups that interact with at least one group selected from CONH, CO, and NH groups include groups with an electronegativity of 1.0 to 4.0 (preferably 1.6 to 3.6, particularly preferably 2.0 to 3.4).

[0153] Examples of such functional groups include substituted or unsubstituted amino groups, carboxyl groups, active methylene groups, nitrile groups, ketone groups, aldehyde groups, ester groups, ether groups, amide groups, hydroxyl groups, halogen groups, sulfonamide groups, etc.

[0154] The molecular weight of the organic compound (X) is, for example, 1000 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.

[0155] The organic compound (X) is preferably a hydrophilic compound, and the logP (octanol / water partition coefficient) value of the organic compound (X) is, for example, -5 or more and 7 or less. From the viewpoint of improving the certainty of the molecular structure, the lower limit of the above-mentioned logP is preferably -3, particularly preferably -1, and the upper limit of the above-mentioned logP is preferably 6, particularly preferably 5, most preferably 4.5, and especially preferably 3.

[0156] It should be noted that the logP value of organic compound (X) can be obtained using commercially available software (e.g., "EPIsuite", a software jointly developed by the US EPA (The Estimations Programs Interface for Windows) and Syracuse).

[0157] (Process 1)

[0158] Step 1 is a step of impregnating the organic compound (X) into the above-mentioned sample forming material and fixing the organic compound (X) in the pores of the above-mentioned sample forming material.

[0159] From the viewpoint of improving the determination rate of molecular structure, it is preferable to select and use crystals with excellent transparency and clear shape (such as needle-like, block-like, or sheet-like shapes) from the metal complex crystals obtained by the above-described method for manufacturing metal complex crystals.

[0160] 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 longer; if the sample forming material is too large, it tends to be difficult for the organic compound (X) to be fully impregnated and the determination rate of the molecular structure decreases.

[0161] 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.

[0162] The metal complex crystals constituting the above-mentioned sample forming material exhibit excellent strength and toughness. Therefore, the pores of the metal complex crystals may or may not be filled with solvent.

[0163] As a method for impregnating the organic compound (X) into the sample forming material and fixing the organic compound (X) within the pores of the sample forming material, the appropriate method can be selected according to the state (liquid, gas, or solid) of the organic compound (X).

[0164] When the organic compound (X) is a liquid, the above-mentioned fixation method can be described as follows: the above-mentioned sample forming material is prepared in a container such as a test tube, the organic compound (X) is added to it, and it is left to stand at -20 to 100°C for 0.25 to 24 hours.

[0165] When the organic compound (X) is a gas, the above-mentioned fixation method can be described as follows: A sealed container, such as a test tube with a cap, is filled with an inert gas (e.g., helium, nitrogen, etc.), and the sample forming material and the organic compound (X) are sealed inside. The container is then allowed to stand at -20 to 100°C for 0.25 to 24 hours. Alternatively, before sealing the container, the sample gas containing the organic compound (X) can be subjected to separation processing using a gas chromatograph or similar method to increase the concentration of the organic compound (X).

[0166] When the organic compound (X) is a solid, the above-mentioned immobilization method can be described as follows: The sample-forming material described above is placed in a container such as a test tube; a solution prepared by dissolving the organic compound (X) in a solvent that is inactive with respect to the organic compound (X) (hereinafter sometimes referred to as "inactive solvent") is added to the solution; and the solution is allowed to stand at -20 to 100°C for 0.25 to 24 hours. Alternatively, after the above-mentioned standing period, the impregnated solution can be concentrated. By performing the concentration treatment, the immobilization rate of the organic compound (X) within the pores increases, and the determination rate of its molecular structure improves.

[0167] The aforementioned sample-forming material exhibits excellent solvent resistance, maintaining its crystal structure in various solvents. Therefore, solvents that improve the certainty of the molecular structure can be selected and used from inert solvents. Examples of such inert solvents include: alcohols such as methanol, ethanol, and isopropanol; tetrahydrofuran (THF), dimethoxyethane, and diethyl ether... Alkane and other chain or cyclic ethers, etc. These can be used alone or in combination of two or more.

[0168] The concentration of organic compound (X) in the solution obtained by dissolving organic compound (X) in an inactive 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.

[0169] Since the sample forming material has amide groups, if an organic compound (X) is impregnated into the sample forming material, the organic compound (X) introduced into the pores of the sample forming material can be firmly fixed by hydrogen bonds.

[0170] Through this process, an X-ray structure analysis sample in which an organic compound (X) is fixed in the pores of the sample forming material can be obtained.

[0171] (Process 2)

[0172] Step 2 is a step of irradiating the X-ray structure analysis sample obtained in the above steps (i.e., the sample formed by fixing the organic compound (X) 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).

[0173] In the above method for determining the molecular structure of organic compound (X), there is no need to crystallize the 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, the molecular structure can be determined by X-ray structure analysis.

[0174] Furthermore, according to the above-mentioned method for determining the molecular structure of organic compound (X), even if organic compound (X) is in a gaseous state, its molecular structure can be determined by X-ray structure analysis.

[0175] Therefore, based on the above-described method for determining the molecular structure of organic compound (X), it is possible to easily determine the structure of trace impurities in drugs, substances that cause odor (including fragrance) (e.g., spices), food additives, and trace components in plants and animals.

[0176] [Method for determining the molecular structure of gaseous odor component (Y)]

[0177] The method for determining the molecular structure of the gaseous odor component (Y) includes the following steps 1, 2 and 3.

[0178] Step 1: Feed a sample gas containing a gaseous odor component (Y) into a gas component separation column, and separate and collect the gaseous odor component (Y).

[0179] Step 2: The gaseous odor component (Y) collected by separation is impregnated 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).

[0180] Step 3: Irradiate the sample forming material (or the metal complex crystal) after fixing the gaseous odor component (Y) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0181] (Process 1)

[0182] Step 1 is a step of supplying a sample gas containing a gaseous odor component (Y) to a gas component separation column, thereby separating and collecting the gaseous odor component (Y). Step 2 is a step of supplying a sample gas containing a gaseous odor component (Y) together with a carrier gas to a gas component separation column, thereby separating and collecting the gaseous odor component (Y) together with the carrier gas.

[0183] The gaseous odor component (Y) is a gaseous organic compound that emits an odor, preferably a compound having the same functional groups and molecular weight as the organic compound (X) mentioned above.

[0184] The sample gas may contain two or more odor components (Y1, Y2, ..., Yn; n represents an integer greater than 2), and may further contain gaseous components other than odor components.

[0185] A column for gas component separation has a stationary phase inside. When a sample gas containing multiple components is supplied to the column along with a carrier gas, it can separate the components by utilizing the different interactions between each component in the sample gas and the stationary phase, resulting in changes in retention time. Helium, nitrogen, or other inert gases are preferred as the carrier gas.

[0186] The chromatographic column can also be connected to a device for separating and collecting the sample gas after separation using the chromatographic column.

[0187] When the sample gas contains two or more gaseous odor components (Y1, Y2, ..., Yn; where n represents an integer of 2 or more), it is preferable to separate and collect the gaseous odor components (Y1), (Y2), ..., and (Yn) separately. Alternatively, the gaseous odor components may be separated and collected together with the carrier gas.

[0188] (Process 2)

[0189] Step 2 is a process in which the gaseous odor component (Y) separated and collected in step 1 is impregnated into the sample forming material and the gaseous odor component (Y) is fixed in the pores of the sample forming material.

[0190] This process can be carried out using the same method as step 1 of the method for determining the molecular structure of the organic compound (X) described above. Through this process, an X-ray structure analysis sample can be obtained, in which a gaseous odor component (Y) is fixed within the pores of the aforementioned metal complex crystal.

[0191] (Process 3)

[0192] Step 3 is to irradiate the X-ray structure analysis sample obtained in the above steps (i.e., the sample formed by fixing the gaseous odor component (Y) in the pores of the sample forming material) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0193] This step can be carried out using the same method as step 2 of the method for determining the molecular structure of the organic compound (X) described above.

[0194] According to the method for determining the molecular structure of the gaseous odor component (Y) described above, the gaseous odor component (Y) can be fixed in a gaseous state on a sample forming material to form an X-ray structure analysis sample. By subjecting the formed X-ray structure analysis sample to X-ray structure analysis, the molecular structure can be easily determined. Furthermore, previously, the causative substances of odors (including fragrances) were determined using olfactory GC-MS, relying on human senses. However, according to the method for determining the molecular structure of the gaseous odor component (Y) described above, the molecular structure of the gaseous odor component (Y) can be accurately determined without relying on human senses.

[0195] The above-described solutions and combinations thereof are merely examples. Without departing from the spirit of this disclosure, appropriate additions, omissions, substitutions, and modifications can be made to the solutions. Furthermore, the various methods disclosed in this specification can be combined with any other features disclosed in this specification. Moreover, this disclosure is not limited to the specific implementation methods.

[0196] Example

[0197] The present disclosure will be described in more detail below through embodiments, but the present disclosure is not limited to these embodiments.

[0198] The single-crystal X-ray structure was analyzed using the following automated single-crystal X-ray diffraction apparatus.

[0199] Single-crystal automated X-ray diffraction apparatus: "XtaLABSynergy Custom", manufactured by Rigaku Corporation.

[0200] Radiation source: Cu-Kα rays (wavelength 0.79 Å)

[0201] Output: 50mA, 24kV

[0202] Example 1 (Preparation of X-ray structural analysis sample forming material containing DMF and water within pores)

[0203] Add the following to a 10 mL screw-top test tube: a carboxylic acid ligand (24.2 mg, 0.1 mol) represented by formula (c2-1-1), a pyridine ligand (31.8 mg, 0.1 mol) represented by formula (p2-1), Zn(NO3)26H2O (29.7 mg, 0.1 mol), and a DMF / H2O (4 mL / 1 mL) mixed solvent, and sonicate to dissolve them.

[0204] Then, the test tube was tightly capped and left to stand at 100°C for 6 hours.

[0205] The solvent in the test tube was removed using a Pasteur pipette, and the process was repeated three times, replacing the solvent with a new DMF / H2O (4 mL / 1 mL) mixed solvent.

[0206] [Chemical Formula 7]

[0207]

[0208] Thus, needle-like or blocky single-crystal particles with transparency and a length of 10-200 μm were obtained. These were used as sample forming material 1. Sample forming material 1 contains DMF and water within its pores.

[0209] The crystal structure of the obtained sample forming material 1 was confirmed by single-crystal X-ray structural analysis. A schematic diagram of sample forming material 1 is shown below. Figure 1 .

[0210] The three-dimensional network structure of the sample forming material 1 was confirmed by single-crystal X-ray structural analysis.

[0211] In addition, it is known that the major axis of the inscribed ellipse of the pores contained in material 1 of the sample is 12 Å and the minor axis is 8 Å.

[0212] Example 2 (Preparation of X-ray structural analysis sample containing ethyl acetate within pores for material 2)

[0213] The solvent was removed from the screw-top test tube containing DMF / H2O (4 mL / 1 mL) and DMF-containing sample forming material 1 obtained by the same method as in Example 1, and replaced with a mixed solvent of ethyl acetate / DMF (1 mL / 4 mL). The tube was left to stand for 1 day.

[0214] Then, the solvent in the test tube was removed and replaced with a mixture of ethyl acetate / DMF (1 mL / 2 mL), and the tube was left to stand for 1 day.

[0215] Next, the solvent in the test tube was removed and replaced with a mixture of ethyl acetate / DMF (1 mL / 1 mL), and the tube was left to stand for 1 day.

[0216] Then, the solvent in the test tube was removed and replaced with a mixture of ethyl acetate / DMF (2 mL / 1 mL), and the tube was left to stand for 1 day.

[0217] Then, the solvent in the test tube was removed, and the process of replacing it with ethyl acetate was repeated three times.

[0218] Thus, needle-like or blocky single-crystal particles containing ethyl acetate within their pores were obtained. These were used as sample forming material 2. Sample forming material 2 contains ethyl acetate within its pores.

[0219] The results of single-crystal X-ray structural analysis of the obtained sample forming material 2 confirmed that it has the same three-dimensional network structure as the sample forming material 1.

[0220] Example 3 (Preparation of X-ray structural analysis sample containing THF within pores, forming material 3)

[0221] The solvent was removed from the screw-top test tube containing ethyl acetate and ethyl acetate in the pores of the sample forming material 2, which was obtained by the same method as in Example 2, and replaced with a THF / ethyl acetate (1 mL / 4 mL) mixed solvent. The tube was then left to stand for 1 day.

[0222] Then, the solvent in the test tube was removed and replaced with a mixture of THF / ethyl acetate (1 mL / 2 mL), and the tube was left to stand for 1 day.

[0223] Next, the solvent in the test tube was removed and replaced with a THF / ethyl acetate (1 mL / 1 mL) mixed solvent, and the tube was left to stand for 1 day.

[0224] Then, the solvent in the test tube was removed and replaced with a THF / ethyl acetate (2 mL / 1 mL) mixed solvent, and left to stand for 1 day.

[0225] Then, the solvent in the test tube was removed, and the process of replacing it with THF was repeated three times.

[0226] Thus, needle-like or blocky single-crystal particles containing THF within their pores were obtained. These were used as sample forming material 3. Sample forming material 3 contains THF within its pores.

[0227] The results of single-crystal X-ray structural analysis of the obtained sample forming material 3 confirmed that it has the same three-dimensional network structure as the sample forming material 1.

[0228] Comparative Example 1 (Preparation of X-ray structural analysis specimen forming material 4)

[0229] First, add 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) (31.3 mg, 0.1 mmol), 21 mL of CHCl3, and 1.7 mL of methanol to a 50 mL sample vial, and sonicate until completely dissolved. Add 4.5 mL of the resulting solution to a screw-top test tube.

[0230] Next, zinc chloride (20.5 mg, 0.15 mmol) and methanol (5 mL) were added to a 10 mL sample vial, and the solution was dissolved by sonication. 1 mL of the resulting solution was then added to the screw-cap test tube described above.

[0231] Then, the screw-top test tube was capped and left to stand at room temperature for 3 days. This yielded transparent, needle-like or blocky single-crystal particles with a length of 10–200 μm. These were used as sample forming material 4.

[0232] Single-crystal X-ray structural analysis of sample forming material 4 was performed. A schematic diagram of sample forming material 4 is shown below. Figure 2 .

[0233] Single-crystal X-ray structural analysis revealed that the major axis of the inscribed ellipse of the pores contained in material 4 of the sample is 13 Å and the minor axis is 10 Å.

[0234] Solvent resistance evaluation

[0235] The solvent resistance of the sample forming material 1 obtained in Example 1 and the sample forming material 4 obtained in Comparative Example 1 was evaluated by the following method.

[0236] Specifically, one single-crystal particle of the sample-forming material was added to a micro-sample vial, along with 1 μL of the solvent described below. The vial was then left to stand at 50°C or room temperature (25°C) for 17 hours, and the preservation of the crystal structure was visually observed after standing. Next, the solvent resistance was evaluated using the following criteria.

[0237] <Soluble Resistance Evaluation Criteria>

[0238] Excellent (○): It can maintain the crystal structure and the framework of the metal complex can be observed by single-crystal X-ray diffraction.

[0239] Good (△): The crystal structure was not maintained after standing at 50°C for 17 hours, but it was able to maintain the crystal structure after standing at room temperature for 17 hours.

[0240] Poor (×): Failed to maintain crystal structure

[0241]

[0242] Example 11 (Structural Determination of Organic Compounds with Ketone Groups)

[0243] 45 μL of THF was added to a microsample vial with a septum cap, and then one single crystal particle of the DMF-containing sample forming material 1 obtained in Example 1 was impregnated therein. The THF was then removed as much as possible using a pipette.

[0244] Next, 1 μg of 4-methylacetophenone was added to the microsample vial. Then, the vial was capped and left to stand at a constant temperature of 50°C for 17 hours.

[0245] Then, sample forming material 1 is removed from the microsample vial. Sample forming material 1 removed from the microsample vial is used as the X-ray structural analysis sample.

[0246] The obtained X-ray structure analysis samples were mounted on an X-ray structure analysis apparatus for crystal structure analysis, and the crystal structure analysis capability was evaluated according to the following evaluation criteria. The results are shown in the table below.

[0247] <Evaluation Criteria for Crystal Structure Resolution>

[0248] ◎(Good): Able to determine the molecular structure very clearly.

[0249] ○ (Qualified): Able to determine the molecular structure with a certain degree of accuracy.

[0250] × (Unqualified): Molecular structure could not be determined.

[0251] Examples 12-14 (Structural determination of organic compounds containing ketone groups)

[0252] The same procedure as in Example 11 was followed, except that an organic compound (X) listed in Table 2 below was used instead of 4-methylacetophenone. The results are shown in the table below.

[0253] In addition, a schematic diagram of the crystal structure of the X-ray structure analysis sample (a metal complex crystal with benzoyl immobilized in the pores) obtained in Example 14 is shown below. Figure 3 (a); A schematic diagram showing the shape of the pores in the X-ray structure analysis sample is shown below. Figure 3 (b); The state in which the NH group constituting the amide group of sample forming material 1 interacts with the oxygen atom of the oxo group of benzoyl is shown in the figure. Figure 3 (c)

[0254] Comparative Examples 11-14 (Structure determination of organic compounds containing ketone groups)

[0255] Sample forming material 4 was used instead of sample forming material 1, and otherwise the procedure was the same as in Examples 11-14. The results are shown in the table below.

[0256]

[0257] Examples 15-27, Comparative Examples 15-27

[0258] Instead of 4-methylacetophenone, organic compounds (X) listed in Tables 3-5 below were used. Otherwise, the procedure was the same as in Example 11, and X-ray structure analysis samples were obtained and crystal structure analysis was performed. The results are shown in the table below.

[0259] In addition, a schematic diagram of the crystal structure of the X-ray structure analysis sample (a metal complex crystal with dibutyl fumarate fixed in the pores) obtained in Example 22 is shown below. Figure 4 (a); A schematic diagram showing the shape of the pores in the X-ray structure analysis sample is shown below. Figure 4 (b); The interaction between the NH group constituting the amide group of sample forming material 1 and the oxygen atom of the oxy group of dibutyl fumarate is shown in the figure. Figure 4 (c)

[0260]

[0261]

[0262]

[0263] Example 28 (Structure determination of odor components)

[0264] For bottled nitrobenzene, 5 mL of gas from its gas phase was separated and collected by aspiration with a syringe and used as the gaseous odor component (Y).

[0265] The collected gaseous odor component (Y) was added to a capped sample vial containing one single crystal particle of sample forming material 1, and the vial was left to stand at 50°C for 2 hours.

[0266] Then, the sample forming material 1 was removed from the sample bottle and used as the sample for X-ray structural analysis.

[0267] The obtained X-ray structure analysis sample was installed in an X-ray structure analysis device and the crystal structure analysis was performed. The overall molecular structure was determined by X-ray diffraction images.

[0268] Example 29 (Structure determination of odor components)

[0269] The sample solution was obtained by dissolving 5 mg of nitrobenzene, which is the odor component, in 1 mL of acetone.

[0270] 5 μL of the sample solution is injected through the injection port 2 of a gas chromatograph separation and collection device of the following specifications. The components that have passed through the chromatographic column 3 are introduced into the separation and collection device 6 through the split section. The components are separated and collected into 6 separation and collection tubes 7 (separation and collection tubes cooled to -70°C) containing 1 single crystal particle of sample forming material 1. The samples are then allowed to stand at 50°C for 17 hours (refer to...). Figure 5 ).

[0271] Then, the sample forming material 1 added to the separation and collection tube 7 is taken out and used as an X-ray structural analysis sample.

[0272] The obtained X-ray structure analysis sample was installed in an X-ray structure analysis device and the crystal structure analysis was performed. The overall molecular structure was determined by X-ray diffraction images.

[0273] <Specifications for Gas Chromatography Separation and Collection Devices>

[0274] Gas chromatography separation and collection device: trade name "VPS-2800", manufactured by GL Sciences.

[0275] Chromatographic column: DB-5MS 30m-0.32mm-0.5μm, manufactured by GL Sciences.

[0276] Column heating temperature: 80℃ (0 min) → 2℃ / min → 140℃ (0 min)

[0277] Carrier gas: Helium

[0278] Column flow rate: 6.58 mL / min

[0279] Example 30 (Structure determination of odor components)

[0280] Alpha-terpineol was used instead of nitrobenzene, and otherwise the procedure was the same as in Example 29. As a result, the molecular structure of α-terpineol was determined by X-ray diffraction.

[0281] Example 31 (Structure determination of odor components)

[0282] Eugenol was used instead of nitrobenzene, and otherwise the procedure was the same as in Example 29. As a result, the molecular structure of eugenol was determined by X-ray diffraction.

[0283] In summary, the scheme disclosed herein and its variations are noted below.

[0284] [1] An X-ray structure analysis specimen forming material, which is a forming material for forming an X-ray structure analysis specimen containing organic compounds in a regular and ordered arrangement, the forming material comprising the following metal complex crystals.

[0285] Metal complex crystal: A metal complex crystal comprising a metal ion and a ligand coordinated to the metal ion, the metal complex crystal having a three-dimensional network structure with regularly ordered pores, the ligand comprising 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]:

[0286] [I] The compound represented by formula (c1) and the compound represented by formula (p1);

[0287] [II] The compound represented by formula (c2) and the compound represented by formula (p2).

[0288] [2] According to the X-ray structural analysis of the sample forming material described in [1], wherein,

[0289] The aforementioned metal ions are selected from zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions.

[0290] [3] The sample forming material is analyzed by X-ray structural analysis according to [1] or [2], wherein,

[0291] The above-mentioned organic compounds possess functional groups that interact with at least one group selected from CONH, CO and NH groups.

[0292] [4] The sample forming material is analyzed by X-ray structural analysis according to [1] or [2], wherein,

[0293] The above-mentioned organic compounds have at least one functional group selected from substituted or unsubstituted amino, carboxyl, active methylene, nitrile, ketone, aldehyde, ester, ether, amide, hydroxyl, halogen, and sulfonamide groups.

[0294] [5] The X-ray structural analysis sample forming material according to any one of [1] to [4], wherein,

[0295] The logP values ​​of the above organic compounds are greater than -5 and less than 7.

[0296] [6] The X-ray structural analysis sample forming material according to any one of [1] to [5], wherein,

[0297] The compound represented by formula (c1) in [I] above is at least one compound selected from the compounds represented by formulas (c1-1) to (c1-4).

[0298] [7] The X-ray structural analysis sample forming material according to any one of [1] to [5], wherein,

[0299] The compound represented by formula (c1) in [I] above is the same compound represented by formula (c1-1).

[0300] [8] The X-ray structural analysis sample forming material according to any one of [1] to [7], wherein,

[0301] The compound represented by formula (p1) in [I] above is at least one compound selected from the compounds represented by formulas (p1-1) to (p1-7).

[0302] [9] The X-ray structural analysis sample forming material according to any one of [1] to [7], wherein,

[0303] The compound represented by formula (p1) in [I] above is at least one compound selected from the compounds represented by formula (p1-1), formula (p1-2), formula (p1-5) and formula (p1-6).

[0304]

[10] The X-ray structural analysis sample forming material according to any one of [1] to [7], wherein,

[0305] The compound represented by formula (p1) in [I] above is the compound represented by formula (p1-1) and / or the compound represented by formula (p1-2).

[0306]

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

[10] , wherein,

[0307] The compound represented by formula (c2) in [II] above is at least one compound selected from the compounds represented by formulas (c2-1) to (c2-5).

[0308]

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

[10] , wherein,

[0309] The compound represented by formula (c2) in [II] above is the compound represented by formula (c2-1) and / or the compound represented by formula (c2-2).

[0310]

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

[10] , wherein,

[0311] The compound represented by formula (c2) in [II] above is the same compound represented by formula (c2-1).

[0312]

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

[13] , wherein,

[0313] The compound represented by formula (p2) in [II] above is at least one compound selected from the compounds represented by formulas (p2-1) to (p2-4).

[0314]

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

[13] , wherein,

[0315] The compound represented by formula (p2) in [II] above is the same compound represented by formula (p2-1).

[0316]

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

[15] , wherein,

[0317] The molar ratio of the carboxylic acid ligand (c) to the pyridine ligand (p) is 30 / 70 to 70 / 30.

[0318]

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

[16] , wherein,

[0319] The ratio of the metal ions to carboxylic acid ligands (c) [metal ion / carboxylic acid ligand (c) molar ratio] is 30 / 70 to 70 / 30.

[0320]

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

[17] , wherein,

[0321] The content ratio of the above metal ions to pyridine ligands (p) [metal ion / pyridine ligand (p); molar ratio] is 30 / 70 to 70 / 30.

[0322]

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

[18] , wherein,

[0323] In the total amount of ligands constituting the above-mentioned metal complex crystals, the combined content of the above-mentioned carboxylic acid ligands (c) and pyridine ligands (p) accounts for more than 50% by weight.

[0324]

[20] A method for determining the molecular structure of an organic compound (X), comprising the following steps 1 and 2,

[0325] Step 1: The organic compound (X) is impregnated into the X-ray structure analysis sample forming material described in any one of [1] to

[19] to fix the organic compound (X) in the pores of the X-ray structure analysis sample forming material;

[0326] Step 2: Irradiate the X-ray structure analysis sample formed by fixing the organic compound (X) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the organic compound (X).

[0327]

[21] A method for determining the molecular structure of a gaseous odor component (Y), comprising the following steps 1, 2, and 3.

[0328] Step 1: Feed a sample gas containing gaseous odor component (Y) into a column for gas component separation, and separate and collect the gaseous odor component (Y);

[0329] Step 2: The gaseous odor component (Y) collected by separation is impregnated into the X-ray structure analysis sample forming material described in any one of [1] to

[19] to fix the gaseous odor component (Y) in the pores of the X-ray structure analysis sample forming material;

[0330] Step 3: Irradiate the X-ray structure analysis sample material after fixing the gaseous odor component (Y) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

[0331]

[22] The following metal complex crystals are used as materials for forming X-ray structure analysis samples of organic compounds.

[0332] Metal complex crystal: A metal complex crystal comprising a metal ion and a ligand coordinated to the metal ion, the metal complex crystal having a three-dimensional network structure with regularly ordered pores, the ligand comprising 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]:

[0333] [I] The compound represented by formula (c1) and the compound represented by formula (p1);

[0334] [II] The compound represented by formula (c2) and the compound represented by formula (p2).

[0335]

[23] According to the use of

[22] as a sample forming material for X-ray structural analysis of organic compounds, wherein,

[0336] The aforementioned metal ions are selected from zinc ions, iron ions, cobalt ions, nickel ions, copper ions, and silver ions.

[0337]

[24] The use as a sample forming material for X-ray structural analysis of organic compounds as described in

[22] or

[23] , wherein,

[0338] The above-mentioned organic compounds possess functional groups that interact with at least one group selected from CONH, CO and NH groups.

[0339]

[25] The use as a sample forming material for X-ray structural analysis of organic compounds as described in

[22] or

[23] , wherein,

[0340] The above-mentioned organic compounds have at least one functional group selected from substituted or unsubstituted amino, carboxyl, active methylene, nitrile, ketone, aldehyde, ester, ether, amide, hydroxyl, halogen, and sulfonamide groups.

[0341]

[26] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[25] , wherein,

[0342] The logP values ​​of the above organic compounds are greater than -5 and less than 7.

[0343]

[27] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[26] , wherein,

[0344] The compound represented by formula (c1) in [I] above is at least one compound selected from the compounds represented by formulas (c1-1) to (c1-4).

[0345]

[28] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[26] , wherein,

[0346] The compound represented by formula (c1) in [I] above is the same compound represented by formula (c1-1).

[0347]

[29] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[28] , wherein,

[0348] The compound represented by formula (p1) in [I] above is at least one compound selected from the compounds represented by formulas (p1-1) to (p1-7).

[0349]

[30] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[28] , wherein,

[0350] The compound represented by formula (p1) in [I] above is at least one compound selected from the compounds represented by formula (p1-1), formula (p1-2), formula (p1-5) and formula (p1-6).

[0351]

[31] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[28] , wherein,

[0352] The compound represented by formula (p1) in [I] above is the compound represented by formula (p1-1) and / or the compound represented by formula (p1-2).

[0353]

[32] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[31] , wherein,

[0354] The compound represented by formula (c2) in [II] above is at least one compound selected from the compounds represented by formulas (c2-1) to (c2-5).

[0355]

[33] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[31] , wherein,

[0356] The compound represented by formula (c2) in [II] above is the compound represented by formula (c2-1) and / or the compound represented by formula (c2-2).

[0357]

[34] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[31] , wherein,

[0358] The compound represented by formula (c2) in [II] above is the same compound represented by formula (c2-1).

[0359]

[35] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[34] , wherein,

[0360] The compound represented by formula (p2) in [II] above is at least one compound selected from the compounds represented by formulas (p2-1) to (p2-4).

[0361]

[36] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[34] , wherein,

[0362] The compound represented by formula (p2) in [II] above is the same compound represented by formula (p2-1).

[0363]

[37] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[36] , wherein,

[0364] The molar ratio of the carboxylic acid ligand (c) to the pyridine ligand (p) is 30 / 70 to 70 / 30.

[0365]

[38] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[37] , wherein,

[0366] The ratio of the metal ions to carboxylic acid ligands (c) [metal ion / carboxylic acid ligand (c) molar ratio] is 30 / 70 to 70 / 30.

[0367]

[39] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[38] , wherein,

[0368] The content ratio of the above metal ions to pyridine ligands (p) [metal ion / pyridine ligand (p); molar ratio] is 30 / 70 to 70 / 30.

[0369]

[40] Use as a sample-forming material for X-ray structural analysis of organic compounds according to any one of

[22] to

[39] , wherein,

[0370] In the total amount of ligands constituting the above-mentioned metal complex crystals, the combined content of the above-mentioned carboxylic acid ligands (c) and pyridine ligands (p) accounts for more than 50% by weight.

[0371] Industrial applicability

[0372] When using the X-ray structural analysis sample forming material disclosed herein, even when the organic compound (X) is too small for single crystallization or is a compound that cannot be single crystallized, and regardless of whether the organic compound (X) is solid, liquid or gas, the molecular structure can be determined by X-ray structural analysis.

Claims

1. An X-ray structure analysis sample forming material, which is a material for forming X-ray structure analysis samples containing organic compounds arranged in a regular and ordered state, the forming material comprising the following metal complex crystals, Metal complex crystal: A metal complex crystal comprising a metal ion and a ligand coordinated to the metal ion, the metal complex crystal having a three-dimensional network structure with regularly ordered arranged pores, the ligand comprising 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] The compound represented by the following formula (c1) and the compound represented by the following formula (p1); [II] The compound represented by formula (c2) below and the compound represented by formula (p2) below, ， In the formula, R 1 R 2 "Same" or "different" refers to groups selected from single bonds, divalent hydrocarbon groups, divalent heterocyclic groups, and divalent groups formed by the linkage of two or more of the above groups. L 1 ~L 4 The same or different indicates a single bond or a linking group.

2. The X-ray structural analysis sample forming material according to claim 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 claim 1 or 2, wherein, The organic compound has a functional group that interacts with at least one group selected from CONH, CO and NH groups.

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

5. The X-ray structural analysis specimen forming material according to claim 1 or 2, wherein, The organic compound has a logP value greater than -5 and less than 7.

6. A method for determining the molecular structure of an organic compound (X), comprising the following steps 1 and 2, Step 1: The organic compound (X) is impregnated into the X-ray structure analysis sample forming material according to claim 1 or 2 to fix the organic compound (X) in the pores of the X-ray structure analysis sample forming material; Step 2: Irradiate the X-ray structure analysis sample formed by fixing the organic compound (X) with X-rays and analyze 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 odor component (Y), comprising the following steps 1, 2, and 3. Step 1: Feed a sample gas containing gaseous odor component (Y) into a column for gas component separation, and separate and collect the gaseous odor component (Y); Step 2: The gaseous odor component (Y) collected by separation is permeated into the X-ray structure analysis sample forming material according to claim 1 or 2, thereby fixing the gaseous odor component (Y) in the pores of the X-ray structure analysis sample forming material; Step 3: Irradiate the X-ray structure analysis sample material after fixing the gaseous odor component (Y) with X-rays and analyze the obtained diffraction data to determine the molecular structure of the gaseous odor component (Y).

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