Sample for crystal structure analysis, sample precursor for crystal structure analysis, method for producing sample for crystal structure analysis, and kit for preparing sample for crystal structure analysis

Abstract

The present invention pertains to a sample for crystal structure analysis, the sample containing a plurality of host molecules, a plurality of co-crystallizable molecules, and a plurality of target molecules. Each of the host molecules has rotational symmetry. Each of the co-crystallizable molecules has a skeleton structure formed of a single ring structure or a skeleton structure formed of a plurality of ring structures and a connection structure connecting the same. The skeleton structure does not have a rotation axis having an order that is the same as the order of the main axis of each of the host molecules.

Description

Crystal structure analysis sample, crystal structure analysis sample precursor, method for manufacturing crystal structure analysis sample, and crystal structure analysis sample preparation kit 【0001】 The present invention relates to a sample for crystal structure analysis, a sample precursor for crystal structure analysis, a method for producing a sample for crystal structure analysis, and a kit for preparing a sample for crystal structure analysis. 【0002】 In recent years, functional materials utilizing host-guest chemistry have attracted attention. For example, Patent Document 1 describes a method for performing crystal structure analysis by regularly arranging molecules of the compound to be analyzed within the pores of a single crystal of a polymer complex and using the resulting guest molecule inclusion complex as a measurement sample (the so-called "molecular structure determination method by crystal sponge method"). 【0003】 Furthermore, Patent Document 2 describes a method for adjusting the guest molecule inclusion ability of a cage-type host molecule by utilizing the interaction between the lid-shaped molecule and the opening of the cage-type host molecule. Patent Document 2 also describes the molecular structure of the lid-shaped molecule-cage-type host molecule-guest molecule complex obtained by crystal structure analysis. As shown in Patent Document 2, among cage-type host molecules, those that crystallize easily are useful as molecules for preparing samples for crystal structure analysis. 【0004】 International Publication No. 2014 / 038220 (US2015 / 0219533) Japanese Patent Publication No. 2022-130321 【0005】 The cage-type host molecule described in Patent Document 2 is a highly symmetric molecule, and therefore crystals containing this cage-type host molecule tend to belong to a space group with high symmetry. For this reason, even when a crystal of a complex containing this cage-type host molecule and a guest molecule is used as a sample for crystal structure analysis, it was sometimes impossible to determine the structure of the guest molecule. In other words, when the symmetry of the framework mainly composed of the cage-type host molecule is high, there are many stable and equivalent states for the guest molecule. Therefore, when the symmetry of the guest molecule is not high, disorder easily occurs in the periodicity of the arrangement of the guest molecule, and it was sometimes impossible to determine its molecular structure. 【0006】The present invention has been made under such circumstances, and an object thereof is to provide a sample for crystal structure analysis containing a cage-type host molecule, a precursor of a sample for crystal structure analysis, a method for producing a sample for crystal structure analysis, and a kit for producing a sample for crystal structure analysis. 【0007】 In order to solve the above problems, the present inventors intensively studied crystals containing a cage-type host molecule. As a result, it was found that when a molecule capable of an affinity interaction with the cage-type host molecule and satisfying specific requirements regarding symmetry is used as a co-crystallizing agent, crystals belonging to a space group of low symmetry are easily obtained, and it becomes easy to determine the structure of the guest molecule, leading to the completion of the present invention. 【0008】 Thus, according to the present invention, there are provided a sample for crystal structure analysis of the following [1] to [5], a precursor of a sample for crystal structure analysis of [6], a method for producing a sample for crystal structure analysis of [7] to [8], and a kit for producing a sample for crystal structure analysis of [9]. 【0009】〔1〕A sample for crystal structure analysis comprising a plurality of host molecules, a plurality of co-crystallizable molecules, and a plurality of target molecules, where each host molecule has one or more openings, one or more wall portions, and an internal space surrounded by the wall portions, and has rotational symmetry, each co-crystallizable molecule is a molecule capable of having an affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and a connecting structure connecting them, and the skeletal structure does not have a rotational axis of the same order as the order of the main axis of the host molecule, the plurality of host molecules contained in the sample for crystal structure analysis are regularly assembled three-dimensionally, all or part of the plurality of host molecules contained in the sample for crystal structure analysis accommodate the whole or a part of the molecule of the target molecule in each internal space, the plurality of target molecules contained in the sample for crystal structure analysis are regularly arranged three-dimensionally. A sample for crystal structure analysis. 〔2〕The sample for crystal structure analysis according to 〔1〕, wherein the host molecule is a polynuclear metal complex. 〔3〕The sample for crystal structure analysis according to 〔2〕, wherein the polynuclear metal complex contains an ion of an element selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt, and a polydentate ligand having a π-conjugated system. 〔4〕The polydentate ligand having a π-conjugated system is represented by the following formula (1) 【0010】 【0011】A sample for crystal structure analysis according to [3], wherein the ligand is represented as follows: (A is an m-valent group having aromaticity. X is a divalent organic group or a single bond directly connecting A and Y. Y is a coordinating atom or a monovalent group containing a coordinating atom. m represents an integer from 2 to 6. Multiple Xs may be different from each other, and multiple Ys may be different from each other.) [5] A sample for crystal structure analysis according to [1], wherein the affinity interaction between the cocrystallizable molecule and the host molecule is one or more interactions selected from the group consisting of hydrophobic interactions, π-π interactions, CH-π interactions, and Coulomb interactions. [6] A sample precursor for crystal structure analysis comprising a plurality of host molecules and a plurality of cocrystallizable molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric; each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and connecting structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule; the plurality of host molecules contained in the sample precursor for crystal structure analysis are arranged regularly in three dimensions; and the plurality of host molecules contained in the sample precursor for crystal structure analysis are in a state in which a target molecule can be accommodated in each of their internal spaces. [7] A method for producing a crystal structure analysis sample according to [1] using the crystal structure analysis sample precursor described in [6], comprising the step (step a-I) of accommodating the target molecule in the internal space of all or some of the host molecules contained in the crystal structure analysis sample precursor, by coexisting the crystal structure analysis sample precursor described in [6] and the target molecule in the same system in the presence or absence of a solvent.[8] A method for producing a crystal structure analysis sample according to [1] using a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric; the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule; the method for producing a crystal structure analysis sample according to [1], comprising the steps of: preparing a solution containing the host molecule, the target molecule, and the cocrystallizable molecule (step b-I); and precipitating a single crystal containing the host molecule containing the target molecule and the cocrystallizable molecule from the solution obtained in step b-I (step b-II). [9] A sample preparation kit for crystal structure analysis comprising a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric, and the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule. 【0012】 According to the present invention, a sample for crystal structure analysis containing a cage-type host molecule, a sample precursor for crystal structure analysis, a method for producing a sample for crystal structure analysis, and a kit for preparing a sample for crystal structure analysis are provided. 【0013】 This figure shows the structure of the molecules contained in the crystal structure analysis sample obtained in Example 1. This figure shows the structure of the molecules contained in the crystal structure analysis sample obtained in Example 2. This figure shows the structure of the molecules contained in the crystal structure analysis sample obtained in Example 3. This figure shows the structure of the molecules contained in the crystal structure analysis sample obtained in Example 4. This figure shows the structure of the molecules contained in the crystal structure analysis sample obtained in Example 5. 【0014】 The present invention will be described in detail below, divided into the following sections: 1) Sample for crystal structure analysis, 2) Sample precursor for crystal structure analysis, 3) Method for manufacturing a sample for crystal structure analysis, and 4) Kit for preparing a sample for crystal structure analysis. 【0015】 1) Sample for Crystal Structure Analysis The sample for crystal structure analysis of the present invention comprises a plurality of host molecules, a plurality of cocrystallizable molecules, and a plurality of target molecules. Each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and has rotational symmetry. Each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule. The plurality of host molecules contained in the sample for crystal structure analysis are arranged regularly in three dimensions. All or some of the plurality of host molecules contained in the sample for crystal structure analysis contain the whole molecule or a part of the target molecule in their respective internal spaces. The plurality of target molecules contained in the sample for crystal structure analysis are arranged regularly in three dimensions. 【0016】In this specification, "molecule" includes not only electrically neutral substances composed of two or more atoms, but also charged substances (ions) composed of two or more atoms. "Host molecule" means a molecule having an opening, a wall, and an internal space, and having the ability to accommodate a target molecule in the internal space. "Opening" means the part that functions as an entrance to the internal space. "Wall" means the part that separates the inside and outside of the host molecule. "Internal space" means the space enclosed by the wall. There are no restrictions on its shape as long as it can accommodate the target molecule, and it may be elongated, for example, like a "pore." "Target molecule" means the molecule of the compound to be analyzed. "Cocrystallizable molecule" means a molecule that, when added to a solution in which a host molecule is dissolved, functions as a cocrystallizing agent (coformer) and causes the formation of a cocrystal. The expressions "multiple host molecules are assembled regularly in three dimensions" and "multiple target molecules are arranged regularly in three dimensions" refer to a state in which the molecular structure of the host molecule or the molecular structure of the target molecule can be determined by crystal structure analysis, respectively. "Housing the target molecule within the internal space" includes not only the state in which the entire target molecule is completely contained within the internal space, but also the state in which a part of the target molecule is contained within the internal space and the remaining part of the target molecule protrudes from the opening. 【0017】 [Host Molecules] Host molecules contained in a sample for crystal structure analysis are molecules having one or more openings, one or more walls, and an internal space surrounded by the walls. 【0018】 An opening is a portion that functions as an entry point for the target molecule into the internal space. The shape and size of the opening are not particularly limited, as long as the target molecule can pass through. When the largest circle inscribed in the opening is considered, its diameter is, for example, 0.1 to 5 nm, preferably 0.3 to 3 nm. The number of openings contained in the host molecule is usually 1 to 10, preferably 1 to 5. 【0019】The wall portion is a part that functions as a wall partitioning the inside and outside of the host molecule. As will be described later, the wall portion may interact favorably with the cocrystallizable molecule. 【0020】 The internal space is the space inside the host molecule and is a part that accommodates the target molecule. As long as the target molecule can be accommodated, the size of the internal space is not particularly limited. The internal space may be partitioned by a molecular chain or the like and have a plurality of small spaces. 【0021】 The sample for crystal structure analysis of the present invention solves the problems caused by the high symmetry of the host molecule. Therefore, usually, a host molecule with high symmetry is used. In the case of an aggregate such as a polynuclear metal complex described later, since self-assembly is an entropically unfavorable phenomenon, in order to compensate for this, there is a tendency to become a molecule with high configurational entropy and high symmetry. Therefore, when the host molecule is a polynuclear metal complex, it is usually suitably used as the host molecule of the sample for crystal structure analysis of the present invention. 【0022】 As will be described later, the crystal used as the sample for crystal structure analysis of the present invention has reduced symmetry by combining a cocrystallizable molecule having appropriate symmetry according to the order of the main axis of the host molecule (the one with the largest order n among the n-fold rotation axes possessed by the host molecule). Therefore, a molecule having rotational symmetry is used as the host molecule. Examples of the rotation axis possessed by the host molecule include a two-fold rotation axis, a three-fold rotation axis, a four-fold rotation axis, a five-fold rotation axis, a six-fold rotation axis, and the like. 【0023】 Examples of the point group of the host molecule include, for example, I where the main axis is a five-fold rotation axis ｈ , I, D ５ｈ , D ５ｄ , D ５ , O where the main axis is a four-fold rotation axis ｈ , O, D ４ｈ , D ４ｄ , D ４ , T where the main axis is a three-fold rotation axis ｈ , T ｄ , T, D ３ｈ , D ３ｄ , D ３ and the like. 【0024】 The overall charge of the host molecule can be positive, negative, or neutral. A positive or negative charge is preferred for the host molecule, as adjusting the combination with cocrystallizable molecules allows for efficient deposition of samples for crystal structure analysis. When using a multinuclear metal complex as described later as the host molecule, the host molecule typically has a positive charge overall because the multinuclear metal complex contains many metal ions. 【0025】 The size of the host molecule is not particularly limited. When the smallest rectangular parallelepiped that can accommodate the host molecule is considered, the length of the longest side of the rectangular parallelepiped is, for example, 0.3 to 15 nm, preferably 1 to 10 nm, and the length of the shortest side is, for example, 0.3 to 15 nm, preferably 0.5 to 10 nm. 【0026】 As a host molecule, a multinuclear metal complex is preferred because its molecular design is relatively easy. A multinuclear metal complex is a metal complex containing two or more metal ions and ligands. Examples of multinuclear metal complexes used as host molecules include three-dimensional metal complexes containing two or more metal ions and ligands having two or more coordinating sites, and having internal space. In this multinuclear metal complex, the wall portion of the host molecule is usually constructed by the ligands and metal ions. 【0027】 The metal ion is not particularly limited as long as it can form a polynuclear metal complex. Preferably, the metal ion is an element selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt, and more preferably an element from Group 8, Group 9, or Group 10 of the periodic table. The valence of the metal ion is not particularly limited, and is usually 1 to 4, preferably 1 to 3, and more preferably 2. 【0028】Ligands include those that constitute the wall of the host molecule (hereinafter sometimes referred to as "ligand (α)") and ligands that perform other roles (such as regulating the charge of a multinuclear metal complex or occupying empty coordination sites of metal ions to suppress polymerization of the multinuclear metal complex) (hereinafter sometimes referred to as "ligand (β)"). 【0029】 A polydentate ligand having a π-conjugated system is preferred as ligand (α). The presence of a π-conjugated ligand in ligand (α) can facilitate affinity interactions with cocrystallizable molecules. Furthermore, the presence of a polydentate ligand in ligand (α) makes it easier to obtain a host molecule with an internal space suitable for accommodating the target molecule. Among polydentate ligands having a π-conjugated system, those containing an aromatic group as a central skeleton are preferred. Polydentate ligands containing an aromatic group as a central skeleton are relatively rigid and have excellent planarity, thus easily maintaining the structure of the host molecule. Examples of ligand (α) include those represented by the following formula (1). 【0030】 【0031】 In formula (1), A is an aromatic m-valent group. X is a divalent organic group or a single bond directly connecting A and Y. Y is a coordinating atom or a monovalent group containing a coordinating atom. m represents an integer from 2 to 6. Multiple Xs may be different from each other, and multiple Ys may be different from each other. 【0032】 The number of atoms (excluding hydrogen atoms) in the group represented by A is usually 6 to 100, preferably 6 to 60, and more preferably 6 to 30. Examples of the group represented by A include a six-membered aromatic ring, a group formed by the single bond linking of multiple six-membered aromatic rings, and a group having a porphyrin skeleton. 【0033】 Examples of six-membered aromatic rings include groups having aromatic rings such as benzene rings, triazine rings, pyridine rings, and pyrazine rings. Six-membered aromatic rings may have substituents other than -(-X-Y). Examples of substituents include alkyl groups having 1 to 10 carbon atoms; halogen atoms such as fluorine atoms, bromine atoms, and chlorine atoms; and so on. 【0034】 The following are examples of bases represented by A, but are not limited to these. Note that "*" represents a bond (a bond position with X). 【0035】 【0036】 【0037】 In the above formula, M represents a metal ion. Examples of metal ions include those similar to those exemplified as metal ions constituting polynuclear metal complexes. Among these, zinc ions are preferred. 【0038】 The number of atoms in the group represented by X (excluding hydrogen atoms) is usually 1 to 30, preferably 2 to 20, and more preferably 2 to 10. Examples of the group represented by X include the divalent group represented by A, a methylene group, an ethylene group, 1,2-ethendiyl, 1,2-ethingiyl (acetylene group), a p-phenylene group, an m-phenylene group, and other hydrocarbon groups, an amide group (-C(=O)-NH-), an ester group (-C(=O)-O-), and an oxymethylene group (-O-CH ２ -), oxyethylene group (-O-CH ２ CH ２ Examples include, but are not limited to, the group represented by X. Furthermore, the group represented by X may be a group formed by the bonding of two or more of these groups. Examples of such groups include, but are not limited to, the following: 【0039】 【0040】 Examples of coordinating atoms represented by Y include oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, etc. The number of atoms in a monovalent group represented by Y (excluding hydrogen atoms) is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10. Examples of monovalent groups represented by Y include pyridyl groups, amino groups, hydroxyl groups, deprotonated amide groups, carboxylate groups, sulfonate groups, phosphonate groups, dithiocarboxylate groups, cyano groups, and groups containing these groups as substituents. Examples of monovalent groups represented by Y include the following: 【0041】 【0042】 The ligand (α) may include, but is not limited to, the following: 【0043】 【0044】 【0045】 【0046】 Ligands other than those represented by equation (1) can also be used as ligand (α). Examples of such ligands include the following: 【0047】 【0048】 Ligand (β) is preferably a ligand with a relatively low molecular weight. Ligands with a low molecular weight are less likely to cause adverse effects such as steric hindrance to the coordination of ligand (α). Examples of ligand (β) include monodentate ligands or chelate ligands. 【0049】 Monodentate ligands used as ligands (β) include oxide ions (O ２－ ) and other divalent anions; hydroxide ions (OH － ), chloride ions (Cl － ), bromide ions (Br － ), iodide ion (I － ), thiocyanate ion (SCN － Examples include monovalent anions such as ), water, ammonia, and electrically neutral coordinating compounds such as monoalkylamines, dialkylamines, and trialkylamines. 【0050】 Examples of chelate ligands used as ligand (β) include, but are not limited to, bidentate chelate ligands such as ethylenediamine, N,N'-dimethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,2-cyclohexanediamine, N,N,N',N'-tetramethyl-1,2-cyclohexanediamine, and 2,2'-bipyridyl. 【0051】By appropriately selecting metal ions, ligand (α), and ligand (β), and utilizing conventionally known methods, multinuclear metal complexes that can be used as host molecules can be synthesized. Furthermore, known multinuclear metal complexes with inclusion ability can be used as host molecules. An example of such a multinuclear metal complex is shown below, along with the ligand (α) that constitutes it. When expressing the ratio of metal ions and ligand (α) constituting the multinuclear metal complex, the metal ion is represented as "M", ligand (α) as "L", and the second ligand (α) as "X" if necessary. 【0052】 【0053】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ４ ] 【0054】 【0055】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ４ ] 【0056】 【0057】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ３ In the ligand represented by L, M represents a metal ion such as a Zn ion. 【0058】 【0059】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ２ X ３ ] 【0060】 【0061】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L １ ] 【0062】 【0063】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M １２ L ２ ] 【0064】 【0065】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M １２ L ４ ] 【0066】 【0067】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratios of the polynuclear metal complex on the left are [M １０ L ４ ] and the main component ratio of the polynuclear metal complex on the right is [M ８ L ４ ] 【0068】 【0069】 In the above formula, Pd represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratios of the polynuclear metal complex on the left are [M ８ L ４ ] and the main component ratio of the polynuclear metal complex on the right is [M ６ L ４ ] 【0070】 【0071】In the above formula, Pt represents a platinum ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ４ L ４ ] 【0072】 【0073】 In the schematic diagram above, the sphere represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M ６ L ２ ] 【0074】 【0075】 In the schematic diagram above, the sphere represents a palladium ion coordinated with a bidentate chelate ligand (e.g., ethylenediamine). The main component ratio of this polynuclear metal complex is [M １２ L ４ ] 【0076】 Details regarding the synthesis methods of these multinuclear metal complexes are described in International Publication No. 2018 / 159692. 【0077】 [Cocrystallizable Molecules] Cocrystallizable molecules contained in a sample for crystal structure analysis are molecules that can interact affinally with host molecules. Because cocrystallizable molecules can interact affinally with host molecules, host molecules and cocrystallizable molecules tend to assemble regularly in the sample for crystal structure analysis. 【0078】 Affinity interactions between cocrystallizable molecules and host molecules include hydrophobic interactions, π-π interactions, CH-π interactions, and Coulomb interactions. Multiple affinity interactions may occur between cocrystallizable molecules and host molecules. Among these, π-π interactions and Coulomb interactions are preferred as affinity interactions between cocrystallizable molecules and host molecules because they are larger interactions. 【0079】Cocrystallizable molecules are preferably those possessing π-conjugated systems or anionic groups. The presence of π-conjugated systems or anionic groups in cocrystallizable molecules facilitates affinity interactions between the cocrystallizable molecule and the host molecule. The π-conjugated system of a cocrystallizable molecule tends to interact with ligands and other components of the host molecule, while the anionic groups tend to interact with metal ions constituting the host molecule. Furthermore, if the host molecule is a polynuclear metal complex, the host molecule as a whole tends to carry a positive charge. In this case, a cocrystallizable molecule possessing anionic groups and carrying a negative charge as a whole can function as a counterion. 【0080】 Examples of anionic groups include carboxylate ion groups, sulfonate ion groups, and phosphate ion groups, with carboxylate ion groups and sulfonate ion groups being preferred. 【0081】 Cocrystallizable molecules have a skeletal structure composed of either a single ring structure or multiple ring structures connected by linking structures. The skeletal structure refers to the central structure of a cocrystallizable molecule, specifically the part where intramolecular motion is restricted by the ring structure. Because cocrystallizable molecules possess this skeletal structure, their molecular structure does not change significantly. Therefore, by selecting a cocrystallizable molecule suitable for the shape of the host molecule, it is possible to fully express affinity interactions between the cocrystallizable molecule and the host molecule. 【0082】 The ring structures that make up the skeletal structure include aromatic ring structures such as monocyclic aromatic rings and fused aromatic rings, as well as alicyclic structures. The linking structures that make up the skeletal structure include single bonds that connect two ring structures, hydrocarbon groups such as ethene-1,1,2,2-tetrayl groups, and quaternary carbon atoms. 【0083】 The cocrystallizable molecules included in the crystal structure analysis sample of the present invention are molecules having a skeletal structure that does not have a rotation axis of the same order as the principal axis of the host molecule. As will be described later, the symmetry of crystals containing such cocrystallizable molecules tends to be low, which can reduce the disorder of the periodicity of the arrangement of target molecules. 【0084】An example of a cocrystallizable molecule is shown below. In the formula, R independently represents a hydrogen atom, a hydrocarbon group, or an anionic group. Therefore, R does not constitute a skeletal structure. 【0085】 The following cocrystallizable molecules have a skeletal structure with two rotation axes. 【0086】 【0087】 The following cocrystallizable molecules have a skeletal structure with three rotational axes. 【0088】 【0089】 The following cocrystallizable molecules have a skeletal structure with a triple rotation axis and a double rotation axis. 【0090】 【0091】 The following cocrystallizable molecules have a skeletal structure with four rotational axes and two rotational axes. 【0092】 【0093】 The following cocrystallizable molecules have a skeletal structure with five rotational axes. 【0094】 【0095】 The following cocrystallizable molecules have a skeletal structure with a five-fold rotation axis and a two-fold rotation axis. 【0096】 【0097】 The following cocrystallizable molecules have skeletal structures with six rotational axes, three rotational axes, and two rotational axes. 【0098】 【0099】 [Target Molecule] The target molecule included in the crystal structure analysis sample of the present invention is a molecule of the compound to be structurally analyzed. The form of the target molecule is not particularly limited and may be in a solid state, liquid state, or gas state at room temperature (20°C). The molecular weight of the target molecule is usually 2,000 or less, preferably 800 or less. There is no particular lower limit for the molecular weight of the target molecule, but it is usually 50 or more. 【0100】[Sample for Crystal Structure Analysis] In the sample for crystal structure analysis of the present invention, multiple host molecules are arranged in a regular three-dimensional manner. All or some of these host molecules contain the entire target molecule or a portion of the target molecule in their respective internal spaces. Furthermore, the target molecules contained in the internal spaces of the host molecules are arranged in a regular three-dimensional manner. Therefore, by performing crystal structure analysis using the sample for crystal structure analysis of the present invention, the molecular structure of the target molecule can be revealed. 【0101】 In particular, in the crystal structure analysis sample of the present invention, a molecule having a skeletal structure that does not have a rotation axis of the same order as the principal axis of the host molecule is used as the cocrystallizable molecule. Therefore, the symmetry of the crystal used as the crystal structure analysis sample of the present invention tends to be low. As a result, the number of stable and equivalent states for the target molecule is reduced, and even when the symmetry of the target molecule is not high, disorder in the periodicity of the arrangement of the target molecule is less likely to occur, and its molecular structure can be elucidated. 【0102】 For example, M has the following structure ６ L ４ The principal axis of the octahedral cage-like molecule is a triple rotation axis. 【0103】 【0104】 Therefore, the crystal structure analysis sample of the present invention, which contains this cage-like molecule as a host molecule, includes, as cocrystallizable molecules, molecules whose skeletal structure does not have a three-fold rotation axis. Examples of such molecules are listed below. 【0105】 【0106】 Furthermore, M has the following structure ２４ L ８ The principal axis of the octahedral cage-like molecule is a quadruple rotation axis. 【0107】 【0108】Therefore, the crystal structure analysis sample of the present invention, which contains this cage-like molecule as a host molecule, includes, as cocrystallizable molecules, molecules whose skeletal structure does not have a four-fold rotation axis. Examples of such molecules are listed below. 【0109】 【0110】 The Bravais lattice of the crystal used as a sample for crystal structure analysis in the present invention is preferably a simple lattice (P). The crystal system is preferably triclinic, monoclinic, or orthorhombic. Among the space groups belonging to these, P1 or P-1, Pc, Pm, P2, P2 / c, P2 / m, P2 １ P2 １ / c, P2 １ / m, P222, P222 １ P2 １ 2 １ 2. P2 １ 2 １ 2 １ This is preferable. Here, the space group is represented using 230 classifications denoted by Hermann-Morgan symbols. 【0111】 In the crystal structure analysis sample of the present invention, it is preferable that each of the multiple cocrystallizable molecules is interposed between two or more host molecules. In this way, the presence of cocrystallizable molecules between multiple host molecules and the affinity interaction between the cocrystallizable molecules and the multiple host molecules aligns the orientation of the host molecules, thereby increasing the crystallinity of the crystal structure analysis sample. 【0112】 By changing the type of cocrystallizable molecule used, the affinity interaction between the cocrystallizable molecule and the host molecule can be altered, potentially allowing for adjustment of the size and properties of the space between the host molecules. This can be used to prepare crystal structure analysis samples that possess both an internal space (hydrophobic space) within the host molecule and a hydrophilic space between the host molecules. 【0113】In the crystal structure analysis sample of the present invention, it is preferable that the host molecule and the cocrystallizable molecule have different charges. Specifically, this includes cases where the overall charge of the host molecule is positive and the overall charge of the cocrystallizable molecule is negative, or where the overall charge of the host molecule is negative and the overall charge of the cocrystallizable molecule is positive. When the host molecule and the cocrystallizable molecule have different charges, the cocrystallizable molecule functions as a counterion of the host molecule, allowing for efficient deposition of the crystal structure analysis sample from the solution. Furthermore, a crystal structure analysis sample in which the host molecule and the cocrystallizable molecule have different charges exhibits excellent stability. 【0114】 The crystal structure analysis sample of the present invention may contain one cocrystallizable molecule or two or more cocrystallizable molecules. 【0115】 The size of the sample for crystal structure analysis is not particularly limited. A crystal suitable for the crystal structure analysis apparatus used should be selected as the sample for crystal structure analysis. For example, when performing crystal structure analysis using a commercially available X-ray crystal structure analyzer, if we consider the smallest rectangular parallelepiped that can accommodate the sample for crystal structure analysis, the length of its long side is usually 10 to 500 μm, preferably 50 to 500 μm, and the length of its short side is usually 10 to 500 μm, preferably 10 to 200 μm. 【0116】 When determining the molecular structure based on the collected diffraction intensity data after irradiating multiple crystal structure analysis samples with synchrotron X-rays, if we consider the smallest rectangular parallelepiped that can accommodate the crystal structure analysis samples, the length of its long side is usually 0.1 to 100 μm, preferably 1 to 100 μm, and the length of its short side is usually 0.1 to 100 μm, preferably 1 to 10 μm. 【0117】 When performing crystal structure analysis by microelectron diffraction, if we consider the smallest possible rectangular parallelepiped that can accommodate the sample for crystal structure analysis, the length of its long side is usually 0.1 to 1000 nm, preferably 1 to 1000 nm, and the length of its short side is usually 0.1 to 100 nm, preferably 0.1 to 10 nm. 【0118】2) Sample Precursor for Crystal Structure Analysis The sample precursor for crystal structure analysis of the present invention comprises a plurality of host molecules and a plurality of cocrystallizable molecules. Each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric. Each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule. The plurality of host molecules contained in the sample precursor for crystal structure analysis are arranged regularly in three dimensions. The plurality of host molecules contained in the sample precursor for crystal structure analysis are in a state in which a target molecule can be accommodated in their respective internal spaces. 【0119】 The sample precursor for crystal structure analysis is the same as the sample for crystal structure analysis, except that the target molecule is not contained within the internal space of the host molecule. 【0120】 The method for producing a sample precursor for crystal structure analysis is not particularly limited. For example, a sample precursor for crystal structure analysis can be obtained by preparing a solution containing a host molecule and a cocrystallizable molecule, and allowing it to stand to precipitate as a single crystal. 【0121】 The concentration of the host molecule in the solution containing the host molecule and the cocrystallizable molecule is usually 0.1 to 50 mM, preferably 5 to 20 mM. The amount of the cocrystallizable molecule in the solution containing the host molecule and the cocrystallizable molecule is usually 0.1 to 10 equivalents, preferably 0.1 to 4 equivalents, relative to the host molecule. The temperature of the solution when precipitating the sample precursor for crystal structure analysis is usually 0 to 80°C, preferably 4 to 50°C. The standing time when precipitating the sample precursor for crystal structure analysis is usually 1 to 240 hours, preferably 1 to 24 hours. 【0122】 3) Method for manufacturing a sample for crystal structure analysis The method for manufacturing a sample for crystal structure analysis according to the present invention is not particularly limited. For example, a sample for crystal structure analysis can be manufactured by the following manufacturing method (A) or manufacturing method (B). 【0123】[Manufacturing Method (A)] Manufacturing method (A) includes a step (step a-I) in which the crystal structure analysis sample precursor and the target molecule are brought into coexistence in the same system, either in the presence or absence of a solvent, thereby accommodating the target molecule in the internal space of all or some of the host molecules contained in the crystal structure analysis sample precursor. 【0124】 "To have a sample precursor for crystal structure analysis and the target molecule coexist in the same system" means to place these components in a state where they can come into contact with each other. Therefore, the "same system" does not necessarily have to be a single-phase system as a whole. 【0125】 One way to coexist a crystal structure analysis sample precursor and a target molecule in the same system in the presence of a solvent is to immerse the crystal structure analysis sample precursor in a solution or suspension formed by dissolving at least a portion of the target molecule in the solvent. It is important that the immersed crystal structure analysis sample precursor does not dissolve in the solution or suspension. For example, a crystal structure analysis sample can be produced by contacting the crystal structure analysis sample precursor with the target molecule using a solvent in which the crystal structure analysis sample precursor does not dissolve, or by utilizing the mother liquor produced when the crystal structure analysis sample precursor was manufactured. 【0126】 Examples of conditions in which a sample precursor for crystal structure analysis and a target molecule coexist in the same system without a solvent include placing the sample precursor in a container containing gaseous target molecules, or immersing the sample precursor in liquid target molecules. 【0127】 After the target molecule comes into contact with the crystal structure analysis sample precursor, the target molecule is accommodated within the internal space of the host molecule constituting the crystal structure analysis sample precursor. At this time, the regular arrangement of each target molecule results in a single-crystal crystal structure analysis sample. 【0128】 The amount of target molecule to be present with the sample precursor for crystal structure analysis is usually 0.1 mol or more, preferably 0.5 mol or more, per 1 mol of host molecule. 【0129】The conditions for accommodating the target molecule within the internal space of the host molecule constituting the sample precursor for crystal structure analysis are not particularly limited. The temperature for accommodating the target molecule within the internal space of the host molecule is usually 0 to 100°C, preferably 20 to 100°C. The time for accommodating the target molecule within the internal space of the host molecule is usually 30 seconds to 72 hours, preferably 0.5 to 24 hours. 【0130】 The solvents used in manufacturing method (A) include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, and nitrobenzene; aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cycloheptane; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide (DMSO); amides such as N,N-dimethylformamide and n-methylpyrrolidone; ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; esters such as methyl acetate, ethyl acetate, ethyl lactate, and ethyl propionate; and water. These solvents can be used individually or in combination of two or more. 【0131】 [Manufacturing Method (B)] Manufacturing method (B) comprises the steps of: preparing a solution containing a host molecule, a target molecule, and a cocrystallizable molecule (step b-I); and precipitating a single crystal containing the target molecule, the host molecule, and the cocrystallizable molecule from the solution obtained in step b-I (step b-II). 【0132】The host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric. The cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule. The details of these molecules are the same as those of the host molecule and cocrystallizable molecule that constitute the sample for crystal structure analysis of the present invention. 【0133】 Step b-I is the step of preparing a solution containing a host molecule, a target molecule, and a cocrystallizable molecule. The order in which the components are mixed and the state of each component (solution state, pure substance state, etc.) are not particularly limited, as long as the desired solution is prepared. For example, the solutions of each component may be mixed simultaneously, or the target molecule may be added in solution or pure substance state to a solution containing the host molecule and the cocrystallizable molecule, or the cocrystallizable molecule may be added in solution or pure substance state to a solution containing the host molecule and the target molecule. 【0134】 The concentration of the host molecule in the solution obtained in step b-I is usually 0.1 to 50 mM, preferably 1 to 20 mM. The amount of cocrystallizable molecules in the solution obtained in step b-I is usually 0.1 to 10 equivalents, preferably 0.1 to 4 equivalents, relative to the host molecule. The amount of target molecules in the solution obtained in step b-I is usually 0.1 equivalents or more, preferably 1 equivalent or more, relative to the host molecule. 【0135】 Step b-II is a step in which a single crystal containing a host molecule containing the target molecule and a cocrystallizable molecule is precipitated from the solution obtained in step b-I. The temperature of the solution when precipitation of the single crystal is usually 0 to 80°C, preferably 4 to 50°C. The standing time when precipitation of the single crystal is usually 1 to 240 hours, preferably 1 to 24 hours. 【0136】 The solvent used in manufacturing method (B) is the same as the solvent used in manufacturing method (A). 【0137】When manufacturing a sample for crystal structure analysis using manufacturing method (B), it is preferable to use the crystal holder described below, as this allows for efficient placement of the sample in the crystal structure analysis apparatus. The crystal holder is an instrument having a crystal fixing part and a shape that allows it to be fixed directly or via other parts to the goniometer of the crystal structure analysis apparatus. 【0138】 The crystal holder has a crystal fixing portion. The crystal fixing portion is where the sample for crystal structure analysis is fixed. The shape of the crystal fixing portion is not particularly limited. Examples include capillary shape, rod shape, wire shape, mesh shape, multi-hole plate shape, dish shape, plate shape, thin film shape, etc. 【0139】 The crystal holder has a shape that allows it to be fixed directly or via other components to the goniometer of a crystal structure analysis apparatus. Because the crystal holder has this shape, the conventional procedure of fixing the crystal structure analysis sample (single crystal) to the tip of a glass rod or inside a capillary, which was performed before crystal structure analysis, can be omitted. 【0140】 Examples of shapes that can be fixed to the goniometer of a crystal structure analysis apparatus include capillary, rod, and plate shapes. However, it is not limited to these. When the shape of the crystal holder that can be fixed to the goniometer of a crystal structure analysis apparatus is capillary or rod-shaped, the crystal holder can be efficiently fixed to the goniometer of the crystal structure analysis apparatus using the goniometer head of a conventional crystal structure analysis apparatus. 【0141】When performing manufacturing method (B) using a crystal holder, by performing step b-II while the solution obtained in step b-I is in contact with the crystal fixing part of the crystal holder, a single crystal (sample for crystal structure analysis) can be deposited on the surface of the crystal fixing part of the crystal holder. For example, if the crystal holder is a capillary, a solution containing a host molecule, a target molecule, and a cocrystallizable molecule can be filled into the capillary using capillary action and left to stand, thereby depositing a single crystal (sample for crystal structure analysis) on the inner wall of the capillary. By using a capillary as a crystal holder, a sample for crystal structure analysis can be manufactured with a small amount of solution. Therefore, this method is preferably used when the target molecule is present in trace amounts. 【0142】 4) Crystalline Solid Preparation Kit The sample preparation kit for crystal structure analysis of the present invention comprises a combination of a host molecule and a cocrystallizable molecule. 【0143】 The host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric. The cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule. The details of these molecules are the same as those of the host molecule and cocrystallizable molecule that constitute the sample for crystal structure analysis of the present invention. 【0144】 The host molecule and co-crystallizable molecule constituting the crystalline solid preparation kit of the present invention may be in a pure substance state or in a solution state. The crystalline solid preparation kit of the present invention may contain two or more host molecules and / or two or more co-crystallizable molecules. 【0145】 By using the crystalline solid fabrication kit of the present invention, samples for crystal structure analysis and precursors for crystal structure analysis can be efficiently produced. 【0146】The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples. 【0147】 [Synthesis Example 1] [{(N,N,N',N'-tetramethylethylenediamine)palladium} ６ (2,4,6-Tris(4-pyridyl)-1,3,5-triazine) ４ Nitrate Synthesis Nitrates of the octahedral metal complex shown below (hereinafter sometimes referred to as "host molecule (i)") were synthesized according to the method described in J. Am. Chem. Soc., 2004, 126, 9172-9173. Host molecule (i) has a three-fold rotation axis as its main axis. 【0148】 【0149】 [Synthesis Example 2] [{(N,N,N',N'-tetramethylethylenediamine)platinum} ９ (2,4,6-Tris(4-pyridyl)-1,3,5-triazine) ６ Nitrate Synthesis Nitrates of the following tripyramidal triangular prismatic metal complex (hereinafter sometimes referred to as "host molecule (ii)") were synthesized according to the method described in J. Am. Chem. Soc., 2024, 146, 32311-32316. Host molecule (ii) has a three-fold rotation axis as its main axis. 【0150】 【0151】 [Synthesis Example 3] Synthesis of 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrakis(sodium benzenesulfonate) 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrakis(sodium benzenesulfonate) (hereinafter sometimes referred to as "cocrystallizable molecule (iii)") was synthesized according to the method described in New J. Chem., 2017, 41, 4747-4749. 【0152】 【0153】[Single-crystal X-ray crystal structure analysis] Single-crystal X-ray crystal structure analysis was performed using a Rigaku Synergy-S diffuser [Cu-Kα rays (wavelength 1.5418 Å)]. 【0154】 [Example 1] A glass capillary with a diameter of approximately 0.3 mm and a length of approximately 5 cm was heated with a burner and processed into a U-shape. Using capillary action, a chloroform solution of peiminine (20 μg) was filled into the bottom (curved part) of the U-shaped glass capillary, and the solvent was evaporated by standing it at 60°C for 2 hours, thereby concentrating the peiminine at the bottom of the U-shaped glass capillary. Using capillary action, an aqueous solution containing host molecule (i) (20 mM) and co-crystallizable molecule (iii) (main axis is a double-rotated axis) (2 mM) was filled into the bottom of the U-shaped glass capillary, and a homogeneous solution was obtained by heating it at 60°C for 10 minutes. Crystals were precipitated inside the glass capillary by standing this U-shaped glass capillary at 20°C for 12 hours. Crystal structure analysis was performed using precipitated crystals (with a long side length of approximately 200 μm). Figure 1 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 1, one pyminin molecule is housed in the internal space of host molecule (i). Furthermore, the cocrystallizable molecule (iii) is present between host molecules (i), and its sulfonate ion portion is interacting favorably with the cationic apex of host molecule (i). The crystal's space group is P1 (the crystal system is triclinic), and since the entire asymmetric unit of four host molecules (i) and three pyminin molecules was observed crystallographically independently and clearly, it was found to be a crystal with sufficiently low symmetry, suitable for crystal structure analysis. 【0155】 【0156】[Example 2] To an aqueous solution of the nitrate of host molecule (ii) (concentration 5 mM, 600 μL), 2.1 equivalents of rifampicin powder relative to host molecule (ii) were added to obtain a suspension. The obtained suspension was stirred at 60°C for 20 minutes, and to the resulting mixture, an aqueous solution of 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (concentration 20 mM, 5 μL, 0.25 equivalents relative to host molecule (ii)) and an aqueous solution of sodium tetrafluoroborate (concentration 200 mM, 30 μL, 15 equivalents relative to host molecule (ii)) were added, and the mixture was heated at 15°C under open conditions for 1 カ The mixture was allowed to stand for a month to precipitate crystals. Crystal structure analysis was performed using the precipitated crystals (with a long side length of approximately 300 μm). Figure 2 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 2, two rifampicin reactant molecules are contained within the internal space of host molecule (ii). Furthermore, the skeletal portion of the 1,3,6,8-pyrenetetrasulfonate ion is in a partially stacked state with the wall of host molecule 1, and the 1,3,6,8-pyrenetetrasulfonate ion interacts affiliatively with the wall of host molecule (ii). The crystal space group is P2. １ 2 １ 2 １ (The crystal system is orthorhombic), and since the entire asymmetric unit, consisting of one host molecule (ii) and two rifampicin reactant molecules, was observed crystallographically independently and clearly, it was determined to be a crystal with sufficiently low symmetry, suitable for crystal structure analysis. 【0157】 【0158】[Comparative Example 1] To an aqueous solution of the nitrate of host molecule (i) (concentration 20 mM, 1 mL), 10 equivalents of 2,4,6-trimethylbenzene-1,3,5-trimethanesulfonate sodium salt powder (see figure below, the main axis is a 3-rotation axis) were added to obtain a suspension. The obtained suspension was stirred at 80°C for 5 minutes, and the solution was left to stand at room temperature for 1 day to precipitate crystals. Crystal structure analysis was performed using the precipitated crystals (long side length approximately 200 μm). The space group of the obtained crystal was P-3c1 (crystal system is hexagonal), and only 1 / 3 molecules of host molecule (ii) were observed crystallographically independently in the asymmetric unit, and the electron density inside the space was not clearly observed. The crystal had high symmetry and was unsuitable for structural analysis of the guest molecule. 【0159】 【0160】 [Comparative Example 2] To an aqueous solution of the nitrate of host molecule (ii) (concentration 5 mM, 600 μL), 2.1 equivalents of rifampicin powder relative to host molecule (ii) were added to obtain a suspension. The obtained suspension was stirred at 60°C for 20 minutes, and the mixture was left open at 5°C for 1 minute. カ The material was left to stand for a month to allow crystals to precipitate. Crystal structure analysis was performed using the precipitated crystals (with a long side length of approximately 500 μm). The resulting crystal space group was P6. ３ The crystal system was hexagonal ( / mmc), and only host molecules (ii) 1 / 12 molecules were observed crystallographically independently in the asymmetric unit, with no clear observation of electron density originating from the guest molecule. The crystal had high symmetry and was unsuitable for structural analysis of the guest molecule. 【0161】[Comparative Example 3] To an aqueous solution of the nitrate of host molecule (ii) (concentration 5 mM, 600 μL), 5 equivalents of liquid geranyllinalool and 10 equivalents of silver nitrate were added relative to the host molecule (ii) to obtain a suspension. After stirring the obtained suspension at room temperature for 1 hour, a mixture of 10 equivalents of sodium 1,3,5-benzenetrimethanesulfonate (see figure below, the main axis is a 3-rotation axis) relative to the host molecule (ii) was left to stand at 5°C under open conditions for 1 week to precipitate crystals. Crystal structure analysis was performed using the precipitated crystals (long side length approximately 200 μm). The space group of the obtained crystal was P-6 (crystal system is hexagonal), and only 1 / 6 molecules of host molecule (ii) were observed crystallographically independently in the asymmetric unit, and the electron density originating from the guest molecule was not clearly observed. The crystal had high symmetry and was unsuitable for structural analysis of the guest molecule. 【0162】 【0163】 [Example 3] Except for using noscapine (molecular weight 413, 100 μg) instead of peiminine in Example 1, crystals were obtained and crystal structure analysis was performed using the same method as in Example 1. Figure 3 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 3, it was found to have a packing structure similar to that of Example 1 and to be a crystal with sufficiently low symmetry suitable for crystal structure analysis. 【0164】 【0165】 [Example 4] Except for using oxymatrine (molecular weight 264, 30 μg) instead of peiminine in Example 1, crystals were obtained and crystal structure analysis was performed using the same method as in Example 1. Figure 4 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 4, it was found to have a packing structure similar to that of Example 1 and to be a crystal with sufficiently low symmetry suitable for crystal structure analysis. 【0166】 【0167】[Example 5] Except for using oridonin (molecular weight 348) instead of peimin in Example 1, crystals were obtained and crystal structure analysis was performed using the same method as in Example 1. Figure 5 shows the molecular structure obtained by crystal structure analysis. As shown in Figure 5, it was found to have a packing structure similar to that of Example 1 and to be a crystal with sufficiently low symmetry suitable for crystal structure analysis. 【0168】

Claims

1. A crystal structure analysis sample comprising multiple host molecules, multiple cocrystallizable molecules, and multiple target molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric; each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule; the multiple host molecules contained in the crystal structure analysis sample are arranged regularly in three dimensions; all or part of the multiple host molecules contained in the crystal structure analysis sample contain the entire molecule or a part of the molecule of the target molecule in their respective internal spaces; and the multiple target molecules contained in the crystal structure analysis sample are arranged regularly in three dimensions.

2. The crystal structure analysis sample according to claim 1, wherein the host molecule is a polynuclear metal complex.

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

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

6. A sample precursor for crystal structure analysis comprising a plurality of host molecules and a plurality of cocrystallizable molecules, wherein each host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric; each cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and connecting structures, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule; the plurality of host molecules contained in the sample precursor for crystal structure analysis are arranged regularly in three dimensions; and the plurality of host molecules contained in the sample precursor for crystal structure analysis are in a state in which a target molecule can be accommodated in each of their internal spaces.

7. A method for producing a crystal structure analysis sample according to claim 1 using a crystal structure analysis sample precursor according to claim 6, comprising the step (step a-I) of accommodating the target molecule in the internal space of all or some of the host molecules contained in the crystal structure analysis sample precursor, by coexisting the crystal structure analysis sample precursor according to claim 6 and the target molecule in the same system in the presence or absence of a solvent.

8. A method for producing a crystal structure analysis sample according to claim 1, using a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric; the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of a plurality of ring structures and linking structures connecting them, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule; the method for producing a crystal structure analysis sample according to claim 1, comprising the steps of: preparing a solution containing the host molecule, a target molecule, and a cocrystallizable molecule (step b-I); and precipitating a single crystal containing the host molecule containing the target molecule and the cocrystallizable molecule from the solution obtained in step b-I (step b-II).

9. A sample preparation kit for crystal structure analysis comprising a combination of a host molecule and a cocrystallizable molecule, wherein the host molecule has one or more openings, one or more walls, and an internal space surrounded by the walls, and is rotationally symmetric, and the cocrystallizable molecule is a molecule capable of affinity interaction with the host molecule, and has a skeletal structure composed of one ring structure or a skeletal structure composed of multiple ring structures and connecting structures, and the skeletal structure does not have a rotation axis of the same order as the principal axis of the host molecule.

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