Alkaline earth metal methanesulfonate compounds, crystals thereof, methods of preparation and uses

Abstract

The application discloses an alkaline earth metal methyl sulfonate compound, a crystal thereof and application, and the chemical formula of the crystal is M y (SO3CH3)X.nH2O, the crystal is crystallized in a central symmetrical space group P21 / n, Pnma, P4 / nmm, P4 / nmm, P21 / n, Pbca or a structure feature thereof is that two-dimensional infinite alkaline earth metal M-SO3CH3 layers are formed by connecting alkaline earth metal atoms M and SO3CH3 through sharing O atoms, and halogen is between the two layers. The introduction of halogen perfects the system of the metal methyl sulfonate. Meanwhile, the system crystal is non-hygroscopic, stable in air, and has good physical properties.

Description

Technical Field

[0001] This invention belongs to the fields of chemical engineering and crystal materials technology, specifically relating to an alkaline earth metal methanesulfonate compound and its crystals, preparation method, and application in chemical raw materials, etc. Background Technology

[0002] Methylsulfonate compounds have become a research hotspot in recent years due to their unique molecular structure and chemical stability. Methylsulfonate crystals possess a wide transmittance range and good thermal stability, and are easily grown via solution methods, making them suitable for large-scale production. Methylsulfonic acid (CH4SO3), as a strong acid, has a unique molecular structure and chemical stability. The sulfonic acid group (-SO3H) in the methylsulfonic acid molecule has strong polarity and hydrophilicity, enabling it to form stable salt compounds with various metal ions. These salt compounds are readily soluble in solution and exhibit good nucleation and growth characteristics during crystal growth, making them suitable for growing high-quality optical crystals via solution methods. However, the variety of methylsulfonate compounds is currently limited, making them difficult to apply to various fields. Summary of the Invention

[0003] To solve the above-mentioned technical problems, the present invention provides a compound, the chemical formula of which is M. y (SO3CH3)X·nH2O;

[0004] Where M is Sr or Ba; X is Cl, Br or I; n is 2 or 4, and y is 1 or 2.

[0005] The present invention also provides the chemical formula M y A method for preparing (SO3CH3)X·nH2O compounds, wherein the method is as follows:

[0006] A compound containing element M, a compound containing element X, and a compound containing a methanesulfonic acid group are mixed and subjected to a hydrothermal reaction to prepare the compound with the chemical formula M. y Compounds of (SO3CH3)X·nH2O.

[0007] According to an embodiment of the present invention, the compound containing element M is selected from at least one of M(OH)2·nH2O, MO, MF2, MCl2·nH2O, MBr2, M(NO3)2, MC2O2, MCO3, M(HCO3)2, and MSO4. For example, the compound containing element M is selected from at least one of Sr(OH)2·nH2O (e.g., Sr(OH)2·8H2O), SrO, SrF2, SrCl2·nH2O, SrCl2, SrBr2, Sr(NO3)2, SrC2O2, SrCO3, Sr(HCO3)2, SrSO4, Ba(OH)2·nH2O (e.g., Ba(OH)2·8H2O), BaO, BaF2, BaCl2·nH2O, BaBr2, Ba(NO3)2, BaC2O2, BaCO3, Ba(HCO3)2, and BaSO4.

[0008] According to embodiments of the present invention, the compound containing element X is selected from RX2, NH4X, NH4HX, and AX, wherein A is Li, Na, K, Rb, or Cs, R is Ca, Sr, or Ba, and X is at least one of Cl, Br, or I. For example, it is SrCl2, BaCl2, NH4Cl, NH4Br, or NH4I.

[0009] According to embodiments of the present invention, the compound containing a methanesulfonic acid group is selected from SO3CH4, ASO3CH3, and R(CH4SO3)2, wherein A is at least one of Li, Na, K, Rb, or Cs; and R is at least one of Ca, Sr, or Ba, preferably SO3CH4. When both the compound containing element M and the compound containing element X are selected from RX2, wherein R is Sr or Ba, the amount added is calculated according to the stoichiometric ratio in the chemical formula, or the amount added is determined according to the following proportions.

[0010] According to an embodiment of the present invention, in the compound containing methanesulfonic acid, the compound containing element X, and the compound containing element M, the molar ratio of methanesulfonic acid, X, and M is (1-6):(1-6):(1-6); preferably (1-3):(1-3):(1-3); exemplary ratios are 1:1:3, 1:1:1, and 3:1:1.

[0011] According to an embodiment of the present invention, the hydrothermal reaction is carried out in a solvent, which may be selected from inorganic solvents, such as water, exemplarily deionized water.

[0012] According to an embodiment of the present invention, the volume ratio of the sum of the masses of the compound containing element X, the compound containing element M, and the compound containing methanesulfonic acid group to the solvent can be (1.5 to 6.5) g: 10 mL, preferably (2.5 to 5) g: 10 mL; an exemplary ratio is 2.5 g: 10 mL.

[0013] According to an embodiment of the present invention, the reaction temperature of the hydrothermal reaction can be 90–220°C, preferably 180–220°C, for example, 180°C, 200°C, or 220°C. Further, the heating rate of the hydrothermal reaction can be 10–30°C / h, exemplarily 10°C / h, 20°C / h, or 30°C / h.

[0014] According to an embodiment of the present invention, the reaction time of the hydrothermal reaction can be 1 to 5 days, preferably 3 to 4 days, with 3 days and 4 days being exemplary.

[0015] According to an embodiment of the present invention, the preparation method further includes: after the hydrothermal reaction is completed, cooling to room temperature at a rate of 10-20°C / h, and evaporating the compound from the reaction solution at 40-60°C.

[0016] The present invention also provides a crystal with the chemical formula M. y (SO3CH3)X·nH2O, that is, the crystal is M y (SO3CH3)X·nH2O crystals.

[0017] According to an embodiment of the present invention, the crystal is Sr(SO3CH3)Cl·4H2O, which belongs to the monoclinic crystal system, has a center of symmetry, and has a space group of P21 / n. α=γ=90°, β=105.585(6)°, Z=4.

[0018] According to an embodiment of the present invention, the crystal is Sr(SO3CH3)Br·4H2O, belonging to the orthorhombic crystal system, having a center of symmetry, and a space group of Pnma. α=β=γ=90°, Z=8.

[0019] According to an embodiment of the present invention, the crystal is Sr(SO3CH3)I·4H2O, belonging to the tetragonal crystal system, having a center of symmetry, and a space group of P4 / nmm. α=γ=90°, β=109.916(4)°, Z=4.

[0020] According to an embodiment of the present invention, the crystal is Ba(SO3CH3)Cl·4H2O, belonging to the tetragonal crystal system, having a center of symmetry, and a space group of P4 / nmm. α=β=γ=90°, Z=2.

[0021] According to an embodiment of the present invention, the crystal is Ba(SO3CH3)Br·4H2O, which belongs to the monoclinic crystal system, has a center of symmetry, and has a space group of P21 / n. α=β=γ=90°, Z=2.

[0022] According to an embodiment of the present invention, the crystal is Ba(SO3CH3)I·2H2O, belonging to the orthorhombic crystal system, having a center of symmetry, and a space group of Pbca. α=β=γ=90°, Z=8.

[0023] According to an embodiment of the present invention, the crystal is Ba2(SO3CH3)3I·4H2O crystal, belonging to the triclinic crystal system, having a center of symmetry, and a space group of [missing information]. α=90.3110(10)°, β=92.8880(10)°, γ=113.2650(10)°, Z=4.

[0024] According to an embodiment of the present invention, the crystal has the following characteristics: Figure 1 The crystal structure shown.

[0025] According to an embodiment of the present invention, the crystal is formed by M atoms and SO3CH3 connected by sharing O atoms to form a two-dimensional infinite M-SO3CH3 layer, while halogen X is located between the two layers.

[0026] According to an embodiment of the present invention, the Sr(CH3SO3)Cl·4H2O crystal has the following properties: Figure 2 The X-ray diffraction pattern shown.

[0027] According to an embodiment of the present invention, the ultraviolet absorption edges of the crystal can reach 183 and 184 nm, respectively.

[0028] The present invention also provides a method for preparing the crystal, characterized in that the method comprises:

[0029] The compound containing element X, the compound containing element M, and the compound containing methanesulfonic acid group are mixed and heated to crystallize, thereby obtaining the crystal.

[0030] Preferably, the compounds containing element X, element M, and methanesulfonic acid groups are selected from those with the chemical formula M. y The choice of preparation method for (SO3CH3)X·nH2O compounds is consistent.

[0031] According to an embodiment of the present invention, the method is carried out in a solvent. The solvent has the meaning as described above.

[0032] According to an embodiment of the present invention, the temperature for the heating crystallization is 180–220°C;

[0033] The heating and crystallization time is 1 to 15 days, preferably 2 to 5 days, with examples being 2 days, 3 days, 4 days or 5 days.

[0034] According to an embodiment of the present invention, the method for preparing the crystal further includes: after the reaction is completed, cooling to room temperature at a rate of 1 to 10 °C / h, and evaporating the crystal at 20-40 °C.

[0035] According to an embodiment of the present invention, the method for preparing the crystal specifically includes the following steps:

[0036] (1) After mixing the compound containing element X, the compound containing element M, the compound containing methanesulfonic acid and the solvent, the mixture is heated to 180-220℃ at a rate of 10-30℃ / h for 1-15 days to crystallize.

[0037] (2) After the reaction, the reaction solution is cooled to room temperature at a rate of 1-10℃ / h, and the crystals are evaporated at 20-40℃.

[0038] The present invention also provides the application of the above-mentioned crystal in photorefractive information processing or as a chemical raw material.

[0039] The beneficial effects of this invention are:

[0040] The inventors have discovered that methanesulfonate compounds, due to their unique molecular structure and chemical stability, have gradually become a hot topic in optical materials research in recent years. Methanesulfonate crystals possess a wide transmittance range and good thermal stability, and are easily grown via solution methods, making them suitable for large-scale production. Specifically, the crystals of this application have the following characteristics:

[0041] (1) This invention provides a novel halogen-containing methanesulfonic acid alkaline earth metal salt compound and its crystal, wherein the crystal crystallizes in the centrosymmetric space group P21 / n, Pnma, P4 / nmm, P4 / nmm, P21 / n, Pbca or Its structural feature lies in the formation of a two-dimensional, infinite layer of alkaline earth metal M-SO3CH3 connected to SO3CH3 via shared O atoms, with halogens positioned between the two layers. The introduction of halogens perfects the metal methanesulfonate system. Furthermore, this system is non-hygroscopic, stable in air, and possesses excellent physical properties.

[0042] (2) The crystal of the present invention has stable physical and chemical properties.

[0043] (3) The preparation methods of the compounds and crystals of the present invention are simple, fast, and low in cost. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the crystal structure of the Sr(SO3CH3)Cl·4H2O crystal of the present invention.

[0045] Figure 2 The crystal structure of Sr(SO3CH3)Cl·4H2O crystal in Example 2-1 is shown in the figure. The X-ray diffraction pattern obtained by fitting is compared with the X-ray diffraction pattern of the sample powder in Example 1. Detailed Implementation

[0046] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0047] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0048] Example 1

[0049] Preparation of Sr(SO3CH3)Cl·4H2O compound:

[0050] (a) Mix SrCl2 (2.378 g), SO3CH4 (0.481 g) and 10 mL of water, place them in a reaction vessel with a polytetrafluoroethylene liner (25 mL), and heat to 180 °C at a rate of 20 °C / h, and keep at the temperature for 2 days.

[0051] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 10-20℃ / h, and after evaporation at 40-60℃, the Sr(SO3CH3)Cl·4H2O compound can be obtained.

[0052] Preparation of Sr(SO3CH3)Br·4H2O compound:

[0053] (a) Mix Sr(OH)2·8H2O (1.329g), NH4Br (0.490g), SO3CH4 (0.481g) and 10mL of water, place them in a reaction vessel with a polytetrafluoroethylene liner (25mL), and heat to 180℃ at a rate of 20℃ / h, and keep at the temperature for 2 days;

[0054] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 10-20℃ / h, and after evaporation at 40-60℃, the Sr(SO3CH3)Br·4H2O compound can be obtained.

[0055] The preparation of Sr(SO3CH3)I·4H2O compounds simply requires replacing the corresponding starting materials in the preparation of Ba(SO3CH3)Br·4H2O. For example, to prepare Sr(SO3CH3)I·4H2O, NH4I is used instead of NH4Br. The preparation of Ba(SO3CH3)I·2H2O compounds...

[0056] (a) Ba(OH)2·8H2O (1.329g), NH4I (2.174g), SO3CH4 (0.481g) and 10mL of water were mixed and placed in a reaction vessel with a polytetrafluoroethylene liner (25mL). The temperature was increased to 180℃ at a rate of 20℃ / h and kept at the temperature for 2 days.

[0057] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 10-20℃ / h, and the compound Ba(SO3CH3)I·2H2O can be obtained after evaporation at 40-60℃.

[0058] Preparation of Ba2(SO3CH3)3I·4H2O compound

[0059] (a) Ba(OH)2·8H2O (1.329g), NH4I (0.725g), SO3CH4 (0.481g) and 10mL of water were mixed and placed in a reaction vessel with a polytetrafluoroethylene liner (25mL). The temperature was increased to 180℃ at a rate of 20℃ / h and kept constant for 2 days.

[0060] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 10-20℃ / h, and the compound Ba2(SO3CH3)3I·4H2O can be obtained after evaporation at 40-60℃.

[0061] The preparation of compounds Ba(SO3CH3)Cl·4H2O and Ba(SO3CH3)Br·4H2O can be achieved simply by replacing the corresponding raw materials in the preparation of Ba(SO3CH3)I·4H2O. For example, to prepare Br(SO3CH3)Br·4H2O, NH4Br can be used instead of NH4I.

[0062] Example 2-1

[0063] Preparation of Sr(SO3CH3)Cl·4H2O crystals:

[0064] (a) Mix SrCl2 (2.378 g), SO3CH4 (0.481 g) and 10 mL of water, place them in a reaction vessel with a polytetrafluoroethylene liner (25 mL), and heat to 180 °C at a rate of 20 °C / h, and keep at the temperature for 2 days.

[0065] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h, and Sr(SO3CH3)Cl·4H2O crystals can be obtained after evaporation at 20-40℃.

[0066] Preparation of Sr(SO3CH3)Br·4H2O crystals:

[0067] (a) Mix Sr(OH)2·8H2O (1.329g), NH4Br (0.490g), SO3CH4 (0.481g) and 10mL of water, place them in a reaction vessel with a polytetrafluoroethylene liner (25mL), and heat to 180℃ at a rate of 20℃ / h, and keep at the temperature for 2 days;

[0068] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h, and Sr(SO3CH3)Br·4H2O crystals can be obtained after evaporation at 20-40℃.

[0069] The preparation of Sr(SO3CH3)I·4H2O crystals simply requires replacing the corresponding raw materials in the preparation of Ba(SO3CH3)Br·4H2O crystals. For example, to prepare Sr(SO3CH3)I·4H2O crystals, NH4I can be used to replace NH4Br. The preparation of Ba(SO3CH3)I·2H2O crystals...

[0070] (a) Ba(OH)2·8H2O (1.329g), NH4I (2.174g), SO3CH4 (0.481g) and 10mL of water were mixed and placed in a reaction vessel with a polytetrafluoroethylene liner (25mL). The temperature was increased to 180℃ at a rate of 20℃ / h and kept at the temperature for 2 days.

[0071] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h, and Ba(SO3CH3)I·2H2O crystals can be obtained after evaporation at 20-40℃.

[0072] Preparation of Ba2(SO3CH3)3I·4H2O crystals

[0073] (a) Ba(OH)2·8H2O (1.329g), NH4I (0.725g), SO3CH4 (0.481g) and 10mL of water were mixed and placed in a reaction vessel with a polytetrafluoroethylene liner (25mL). The temperature was increased to 180℃ at a rate of 20℃ / h and kept constant for 2 days.

[0074] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h. After evaporation at 20-40℃, Ba2(SO3CH3)3I·4H2O crystals can be obtained.

[0075] A schematic diagram of the structure of the Sr(SO3CH3)Cl·4H2O crystal prepared in this embodiment is shown below. Figure 1 As shown, the unit cell parameters are: Sr(SO3CH3)Cl·4H2O crystal: monoclinic system, with a center of symmetry, space group P21 / n. α=γ=90°, β=105.585(6)°, Z=4.

[0076] Example 2-2

[0077] Preparation of Sr(SO3CH3)Br·4H2O crystals:

[0078] (a) Mix Sr(OH)2·8H2O (1.329g), NH4Br (0.490g), SO3CH4 (0.481g) and 10mL of water, place them in a reaction vessel with a polytetrafluoroethylene liner (25mL), and heat to 180℃ at a rate of 20℃ / h, and keep at the temperature for 2 days;

[0079] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h, and Sr(SO3CH3)Br·4H2O crystals can be obtained after evaporation at 20-40℃.

[0080] Sr(SO3CH3)Br·4H2O crystals were prepared. These crystals belong to the orthorhombic crystal system, have a center of symmetry, and have the space group Pnma. α=β=γ=90°, Z=8.

[0081] Example 2-3

[0082] The difference between Example 2-3 and Example 2-2 is that NH4I is used instead of NH4Br.

[0083] Sr(SO3CH3)I·4H2O crystals were prepared. These crystals are tetragonal, have a center of symmetry, and have a space group of P4 / nmm. α=γ=90°, β=109.916(4)°, Z=4.

[0084] Examples 2-4

[0085] The difference between Example 2-4 and Example 2-2 is that Ba(OH)2·8H2O is used to replace Sr(OH)2·8H2O, and NH4Cl is used to replace NH4Br.

[0086] Ba(SO3CH3)Cl·4H2O crystals were prepared. These crystals are tetragonal, have a center of symmetry, and have a space group of P4 / nmm. α=β=γ=90°, Z=2.

[0087] Examples 2-5

[0088] The difference between Example 2-5 and Example 2-2 is that Ba(OH)2·8H2O is used instead of Sr(OH)2·8H2O.

[0089] Ba(SO3CH3)Br·4H2O crystals were prepared. These crystals are monoclinic, have a center of symmetry, and belong to the space group P21 / n. α=β=γ=90°, Z=2.

[0090] Examples 2-6

[0091] Preparation of Ba(SO3CH3)I·2H2O crystals

[0092] (a) Ba(OH)2·8H2O (1.329g), NH4I (2.174g), SO3CH4 (0.481g) and 10mL of water were mixed and placed in a reaction vessel with a polytetrafluoroethylene liner (25mL). The temperature was increased to 180℃ at a rate of 20℃ / h and kept at the temperature for 2 days.

[0093] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h, and Ba(SO3CH3)I·2H2O crystals can be obtained after evaporation at 20-40℃.

[0094] Ba(SO3CH3)I·2H2O crystals were prepared, which belong to the orthorhombic crystal system, have a center of symmetry, and have the space group Pbca. α=β=γ=90°, Z=8.

[0095] Examples 2-7

[0096] Preparation of Ba2(SO3CH3)3I·4H2O crystals

[0097] (a) Ba(OH)2·8H2O (1.329g), NH4I (0.725g), SO3CH4 (0.481g) and 10mL of water were mixed and placed in a reaction vessel with a polytetrafluoroethylene liner (25mL). The temperature was increased to 180℃ at a rate of 20℃ / h and kept constant for 2 days.

[0098] (b) After the reaction is complete, the temperature is lowered to room temperature at a rate of 1-10℃ / h, and Ba2(SO3CH3)3I·4H2O crystals can be obtained after evaporation at 20-40℃.

[0099] Ba2(SO3CH3)3I·4H2O crystals were prepared, which are triclinic crystals with a center of symmetry and a space group of . α=90.3110(10)°, β=92.8880(10)°, γ=113.2650(10)°, Z=4.

[0100] Example 3

[0101] Examples 2-1 to 2-7: Structural analysis and phase analysis of crystals

[0102] The crystal samples prepared in Examples 2-1 to 2-7 were structurally analyzed using single-crystal X-ray diffraction. The crystal structures of Examples 2-1 to 2-7 were determined using a Bruker SMART APEXⅢ CCD diffractometer with single-crystal X-ray diffraction equipment and Mo Kα radiation. Recording was performed at 293(2) K, with a scanning mode of ω = 2θ. Data were processed using the Multi-Scan method for absorption correction. Structural analysis was performed using the SHELXTL package; the positions of heavy atoms were determined using the direct method, and the coordinates of the remaining atoms were obtained using the difference Fourier synthesis method; F-based... 2 The coordinates of all atoms and the anisotropic thermal parameters were refined using the full matrix least squares method. The chemical formulas of the crystals obtained in Examples 2-1 to 2-7 are Sr(SO3CH3)Cl·4H2O, Sr(SO3CH3)Br·4H2O, Sr(SO3CH3)I·4H2O, Ba(SO3CH3)Cl·4H2O, Ba(SO3CH3)Br·4H2O, Ba(SO3CH3)I·2H2O, and Ba2(SO3CH3)3I·4H2O, respectively.

[0103] Powder X-ray diffraction (XRD) was used to analyze the phases obtained in Examples 1-2. Powder XRD data for each compound in Example 1 and the crystal in Example 2 were acquired using a SmartLab 9KW powder XRD instrument with Cu-Kα radiation, within the range of 5°–70° (2θ), with a step width of 0.01° and a step size of 2s. The XRD data showed that the diffraction peak positions of the samples in Examples 1-3 were essentially the same.

[0104] like Figure 2 As shown, the X-ray diffraction pattern obtained by fitting the crystal structure of Sr(SO3CH3)Cl·4H2O crystal from Example 2-1 is basically consistent with the peak position and intensity of the X-ray diffraction pattern of the sample powder from Example 1. This indicates that the single crystal prepared in Example 2-1 of the present invention is a single pure phase with high purity.

[0105] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A crystal, characterized in that, The chemical formula of the crystal is M y (SO3CH3)X nH2O, that is, the crystal is M y (SO3CH3)X nH₂O crystals; M is Sr or Ba; X is Cl, Br, or I; n is 2 or 4, y is 1 or 2; specifically selected from: The crystal is Sr(SO3CH3)Cl 4H₂O crystal belongs to the monoclinic crystal system, has a center of symmetry, space group P21 / n, a=11.8351(18). b=7.1398(12) c=11.8718(15) α=γ=90 o , β=105.585(6) o Z=4; Alternatively, the crystal is Sr(SO3CH3)Br 4H₂O crystal belongs to the orthorhombic crystal system, has a center of symmetry, and its space group is Pnma, a = 14.3431(3). b=19.5479(4) c=7.1472(2) α=β=γ=90 o Z=8; Alternatively, the crystal is Sr(SO3CH3)I. 4H₂O crystal belongs to the tetragonal crystal system, has a center of symmetry, space group P⁴ / nmm, a = 12.4444(4) b=7.1552(2) c=12.5960(4) α=γ=90 o , β=109.916(4) o Z=4; Alternatively, the crystal is Ba(SO3CH3)Cl. 4H₂O crystal belongs to the tetragonal crystal system, has a center of symmetry, space group P⁴ / nmm, and a = 7.3664(11). b=7.3664(11) c=9.6237(15) α=β=γ=90 o Z=2; Alternatively, the crystal is Ba(SO3CH3)I. 2H₂O crystal belongs to the orthorhombic crystal system, has a center of symmetry, space group Pbca, a=12.0944(2). b=7.66330(10) c=19.4291(4) α=β=γ=90 o Z=8; Alternatively, the crystal is Ba2(SO3CH3)3I. 4H₂O crystal belongs to the triclinic crystal system, has a center of symmetry, and its space group is P. a = 11.7823(4) b=12.1515(4) c=14.8599(4) , α=90.3110(10) o , β=92.8880(10) o , γ=113.2650(10) o Z=4; The method for preparing the crystal is as follows: A compound containing element X, a compound containing element M, and a compound containing methanesulfonic acid groups are mixed and heated to crystallize, thereby obtaining the crystal. The temperature for heat crystallization is 180~220℃; the time for heat crystallization is 1~15 days.

2. The crystal according to claim 1, characterized in that, The crystal is formed by M atoms and SO3CH3 connected by shared O atoms to form a two-dimensional infinite M-SO3CH3 layer, with halogen X between the two layers.

3. The crystal according to claim 1, characterized in that, The compound containing element X is selected from NH4X, NH4HX, wherein X is at least one of Cl, Br or I.

4. The crystal according to claim 3, characterized in that, The compound containing element X is selected from NH4Cl, NH4Br, or NH4I.

5. The crystal according to claim 1, characterized in that, The compound containing element M is selected from M(OH)2. nH2O, MO, MF2, MCl2 At least one of nH2O, MBr2, M(NO3)2, MC2O2, MCO3, M(HCO3)2, and MSO4.

6. The crystal according to claim 5, characterized in that, The compound containing element M is selected from Sr(OH)2. nH2O, SrO, SrF2, SrCl2 nH2O, SrCl2, SrBr2, Sr(NO3)2, SrC2O2, SrCO3, Sr(HCO3)2, SrSO4, Ba(OH)2 nH2O, BaO, BaF2, BaCl2 At least one of nH2O, BaBr2, Ba(NO3)2, BaC2O2, BaCO3, Ba(HCO3)2, and BaSO4.

7. The crystal according to claim 1, characterized in that, The compound containing the methanesulfonic acid group is selected from SO3CH4.

8. The crystal according to claim 1, characterized in that, In the compounds containing methanesulfonic acid, compounds containing element X, and compounds containing element M, the molar ratio of methanesulfonic acid, X, and M is (1~6):(1~6):(1~6).

9. The crystal according to claim 1, characterized in that, The method is carried out in a solvent, which is selected from inorganic solvents.

10. The application of the crystal according to any one of claims 1-8 in the field of photorefractive information processing or as a chemical raw material.

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