Polymorph of pyridoimidazole compound, and preparation method therefor and use thereof

Abstract

The present invention belongs to the technical field of agriculture, and specifically relates to a polymorph of a pyridoimidazole compound, and a preparation method therefor and the use thereof. Crystal form I of compound I provided by the present invention exhibits good thermal storage stability. When formulated into an aqueous suspending concentrate, the crystal form is easy to store, and exhibits a low water separation rate, a high suspension rate, and good formulation fluidity. Moreover, the product has a particle size at the nanometer level. Benefiting from the small-size effect, the product exhibits better adhesion to leaves and pest mites, higher liquid retention, faster penetration and absorption due to the small particle size, more rapid efficacy, and high resistance to rainwater washing.

Description

Polymorphs of pyridine-imidazolium compounds, their preparation methods and applications

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202510306774.5, filed on March 15, 2025, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention belongs to the field of agricultural technology, specifically relating to a polymorph of a pyridine-imidazolium compound, its preparation method, and its application. Background Technology

[0004] Pests and mites damage hundreds of plant species, especially vegetables, flowers, and fruit trees, causing severe economic losses. Pyridine-imidazole derivatives containing heterocyclic compounds possess unique insecticidal activity in modern crop and animal protection.

[0005] Although this compound exhibits outstanding insecticidal and acaricidal effects, its practical applications still face challenges due to certain physicochemical properties. Therefore, finding a simple and effective way to improve its physicochemical properties and further enhance its insecticidal and acaricidal efficacy is crucial for the compound's development and application. Currently used methods for altering its properties typically require changes to its structure or the addition of adjuvants, which are not only costly but also have uncertain effectiveness. Therefore, a method to improve the physicochemical properties and biological activity of the compound and its formulations is urgently needed. Summary of the Invention

[0006] The purpose of this invention is to improve the physicochemical properties of compounds as shown in Formula I, and to improve the bioavailability, solubility, chemical and physical stability, density or flowability of the compounds, so as to enable them to better exert their insecticidal and acaricidal activities and facilitate their preparation in the pesticide formulation process.

[0007] To achieve the above-mentioned technical objectives, the first aspect of the present invention provides a crystalline form I of a pyridine-imidazolium compound, wherein the pyridine-imidazolium compound has the structure shown in Formula I:

[0008] The crystal form I exhibits at least three of the following diffraction peaks given as 2θ values ​​in its X-ray powder diffraction pattern: 6.02, 6.20, 6.28, 6.50, 10.06, 11.76, 14.86, 17.02, 18.48, 18.62, 19.56, 19.68, 21.38, 24.88, 28.58, 29.76, 31.72, 32.80, 37.64, 38.06, 38.48, 41.26, 44.20, 44.50, and 44.98, with each 2θ value having an error range within ±0.2°.

[0009] Furthermore, the crystal form I exhibits at least three of the following diffraction peaks given by 2θ values ​​in the X-ray powder diffraction pattern: 6.02, 6.28, 10.06, 11.76, 14.86, 17.02, 18.48, 18.62, 19.68, 21.38, 28.58, 29.76, and 44.20, wherein the error range of each 2θ value is within ±0.2°.

[0010] Furthermore, the crystal form I exhibits at least three of the following diffraction peaks given as 2θ values ​​in the X-ray powder diffraction pattern: 6.02, 6.28, 10.06, 18.48, 18.62, 21.38, and 44.20, wherein the error range of each 2θ value is within ±0.2°.

[0011] Furthermore, the crystal form I has an X-ray powder diffraction pattern as shown in Figures 1-3.

[0012] A second aspect of the present invention provides a method for preparing crystal form I of a pyridine-imidazole compound, the method comprising the following steps:

[0013] Compound I was added to solvent A, heated and stirred until dissolved, then filtered. The filtrate was allowed to stand to allow the solvent to evaporate. The precipitated solid was then filtered, washed, and dried to obtain a white crystalline solid.

[0014] The pyridine-imidazolium compound has the structure shown in Formula I:

[0015] Solvent A is selected from one or more of ethyl acetate, tetrahydrofuran, and acetonitrile.

[0016] Furthermore, the mass-volume ratio of compound I to solvent A in g / mL is 1:20-60, for example, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, and any value within the range of any two values, preferably 1:20.

[0017] Furthermore, the heating and stirring conditions include: heating and stirring in a 50°C water bath for 3 hours.

[0018] Furthermore, the crystalline form I of the pyridine-imidazole compound is the crystalline form I of the pyridine-imidazole compound described in the first aspect above, as specifically described in the first aspect.

[0019] The third aspect of the present invention provides an insecticidal and acaricidal composition comprising crystal form I as described in the first aspect or crystal form I prepared by the preparation method described in the second aspect, wherein the weight percentage of crystal form I is 1%-50%.

[0020] Furthermore, the insecticidal and acaricidal composition further includes component B, wherein the weight percentage of component B is 1%-50%; the insecticidal and acaricidal composition also includes agriculturally or forestry-acceptable adjuvants or carriers.

[0021] Furthermore, component B is selected from the following substances: butylated urea, triazole tin, tricyclic tin, phenylbutylated tin, propargite, trichlorfon, bromonitrile dimethyl dimethoate, acetamiprid, acetamiprid, fipronil, pyridaben, pyrazopyridine, flupyrazole, butenpyram, isoxaflutole, cyproconazole, flerosulfanil, afolanar, fluoxazolamide, oxazolidinyl, sarolaner, lotelanar, sarolaner, flusulfanilamide, amphetamine, avermectin, emamectin benzoate The following are some of the following: salt, spinosad, ethyl spinosad, tetradifon, thiamethoxam, etoxazole, flufenoxam, flufenoxuron, flupentiofenox, sulfiflumin, flufenoxuron, benzylpyridinium, pyridaben, azoxystrobin, pyrimethanil, pyridaben, azoxystrobin, acetamiprid, etoxazole, cyprodinil, diflubenzuron, bifenazate, pyrimethanil, flometoquin, flufenoxuron, spirodiclofen, spirotetramat, or spirodiclofen.

[0022] Furthermore, the formulation of the insecticidal and acaricidal composition is selected from suspension concentrates, soluble granules, suspension seed dressing agents, granules, microparticles, or water-dispersible granules.

[0023] Furthermore, the suspending agent is selected from water-based suspending agents or oil-based suspending agents.

[0024] Furthermore, in the water-based suspending agent, the weight percentage of crystal form I is between 1% and 50%, and it also includes a dispersant with a weight percentage between 1% and 20%, a wetting agent with a weight percentage between 1% and 20%, a thickener with a weight percentage between 0.01% and 10%, a preservative with a weight percentage between 0.01% and 10%, an antifreeze agent with a weight percentage between 1% and 20%, and the balance being water.

[0025] Furthermore, the dispersant is selected from at least one of SOPROPHOR SC, styrene-phenol polyoxyethylene ether phosphate ammonium salt, tristyrene-phenol polypropylene-polyethylene block polyether, sodium, calcium, or ammonium salt of lignin sulfonic acid (optionally polyethoxylated), sodium or ammonium salt of maleic anhydride copolymer, sodium salt of condensed phenol sulfonic acid, ammonium salt of polyarylphenyl ether sulfate, or naphthalene sulfonate formaldehyde condensate.

[0026] Furthermore, the wetting agent is selected from at least one of NS-500LQ, isotridecyl alcohol polyoxyethylene ether, alkyl sulfosuccinate, laurate, alkyl sulfate, phosphate ester, alkynyl glycol, ethoxyfluorinated alcohol, ethoxylated silicone, alkylphenol ethoxylate, benzene sulfonate, alkyl-substituted benzene sulfonate, alkyl α-olefin sulfonate, naphthalene sulfonate, alkyl-substituted naphthalene sulfonate, naphthalene sulfonate or alkyl-substituted naphthalene sulfonate condensate with formaldehyde, 2-ethylhexyl propyl glycol ether or alcohol ethoxylate.

[0027] Furthermore, the thickener is selected from at least one of magnesium aluminum silicate, guar gum, pectin, casein, carrageenan, xanthan gum, alginate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, or carboxymethylcellulose.

[0028] Furthermore, the preservative is selected from BIT.

[0029] Furthermore, the antifreeze is selected from at least one of liquid polyols, preferably ethylene glycol, propylene glycol or glycerin.

[0030] The fourth aspect of the present invention provides the use of crystal form I as described in the first aspect, crystal form I prepared by the preparation method described in the second aspect, or the insecticidal and acaricidal composition described in the third aspect in controlling insect pests and mites.

[0031] The beneficial effects of this invention are as follows: The crystalline form I of the pyridine-imidazolium compound provided by this invention has excellent thermal storage stability. When prepared as an aqueous suspension, it is easy to store, exhibits low water separation rate, high suspension rate, and good formulation flowability. Simultaneously, the product particle size reaches the nanoscale, resulting in better adhesion to leaves and mites due to the small-scale effect, higher pesticide retention, faster penetration and absorption due to the smaller particle size, more rapid efficacy, and high resistance to rain washout. Attached Figure Description

[0032] Figure 1 is an X-ray powder diffraction pattern of the crystalline powder of Example 2 of the present invention;

[0033] Figure 2 is an X-ray powder diffraction pattern of the crystalline powder of Example 3 of the present invention;

[0034] Figure 3 is an X-ray powder diffraction pattern of the crystalline powder of Example 4 of the present invention. Detailed Implementation

[0035] The following embodiments are intended to enable those skilled in the art to more fully understand the present invention, but are not intended to limit the invention to the scope of the embodiments described.

[0036] The X-ray powder diffraction pattern of crystal form I of the pyridine-imidazole compound in this invention was obtained by X-ray powder diffraction, and the specific determination method is as follows:

[0037] With CuKα radiation ( The X-ray source was a tube with a voltage of 40 kV and a current of 30 mA. The sample was prepared by dry pressing. An appropriate amount of sample was placed flat on the sample stage and the background of the blank sample stage was subtracted before testing. The test was conducted at room temperature. The test parameters were as follows: distance from sample to detector: 30 cm, scanning range: 5-40° (2θ value), scanning step size: 0.02°, step dwell time: 0.12 s, and scanning speed: 5° / min.

[0038] After the test is completed, the instrument data processing system digitizes and plots the received diffraction angle (2θ) and corresponding diffraction intensity, generating an X-ray powder diffraction pattern. At the same time, the system automatically extracts the key data of each diffraction peak in the pattern: the 2θ value, diffraction intensity, and d value (interplanar spacing) of the diffraction peak, and calculates the relative intensity of each diffraction peak (with the intensity of the strongest diffraction peak in the pattern as 100%, and the ratio of the intensity of the other diffraction peaks to the strongest peak), finally forming the diffraction data table as shown in Table 1, which corresponds to Figure 1.

[0039] Example 1

[0040] Preparation method of compound I:

[0041] The specific preparation process is as follows:

[0042] (1) The first solvent (pyridine, 15 mL) was added to the reaction flask, followed by the condensing agent (EDCI, 12 mmol) and the first basic substance (DMAP, 1.6 mmol). Compound I-1 and compound 3,5-di-tert-butylbenzoic acid (8 mmol) were added and reacted at room temperature for 3 h to carry out the first reaction. Then, water was added, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. The mixture was filtered and the filtrate was concentrated under reduced pressure to obtain compound I-2.

[0043] (2) The obtained compound I-2 was dissolved in a second solvent (glacial acetic acid, 20 mL), and the reaction was carried out under reflux at 117.9 °C for 4 h to carry out the second reaction. After cooling to room temperature, the pH of the system was adjusted to 9 by adding sodium hydroxide aqueous solution, and then extracted with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain compound I-3;

[0044] (3) Compound I-3 was dissolved in a third solvent (THF, 20 mL), and a second basic substance (0.76 g of mineral oil-coated NaH, NaH content 60 wt%, NaH content 19 mmol) was added. After reacting at room temperature for 10 min, an ethyl sulfonyl compound (ethyl sulfonyl chloride, 19 mmol) was added, and the reaction was carried out at room temperature for 12 h. The mixture was quenched with saturated ammonium chloride, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained product was purified by column chromatography to obtain compound I (2.5 g), a white solid. X-ray powder diffraction analysis confirmed that the white solid was amorphous.

[0045] Example 2

[0046] 0.5 g of compound I prepared in Example 1 was placed in a 100 mL round-bottom flask. 10 mL of ethyl acetate was added to the active pharmaceutical ingredient powder. The mixture was heated and stirred in a water bath at 50 °C for 3 h, then filtered. The filtrate was allowed to stand for 7 days to allow the solvent to evaporate. The precipitated solid was filtered, washed, and dried to obtain a white crystalline solid with a yield of 56.8% and a purity of 99.16%. The X-ray powder diffraction pattern of the white crystalline solid is shown in Figure 1, and the data are shown in Table 1. It is named crystal form I.

[0047] Table 1: X-ray powder diffraction data of crystal form I (ethyl acetate)

[0048] Example 3

[0049] 0.5 g of compound I prepared in Example 1 was placed in a 100 mL round-bottom flask. 10 mL of acetonitrile was added to the raw drug powder, and the mixture was heated and stirred in a water bath at 50 °C for 3 h. After filtration, the filtrate was allowed to stand for 7 days to allow the solvent to evaporate. The precipitated solid was filtered, washed, and dried to obtain a white crystalline solid with a yield of 44.6% and a purity of 99.31%. The X-ray powder diffraction pattern of the white crystalline solid, as shown in Figure 2, was determined to be crystal form I.

[0050] Example 4

[0051] 0.5 g of compound I prepared in Example 1 was placed in a 100 ml round-bottom flask. 10 mL of tetrahydrofuran was added to the raw material powder, and the mixture was heated and stirred in a water bath at 50 °C for 3 h. After filtration, the filtrate was allowed to stand for 7 days to allow the solvent to evaporate. The precipitated solid was filtered, washed, and dried to obtain a white crystalline solid with a yield of 59.1% and a purity of 99.03%. The X-ray powder diffraction pattern of the white crystalline solid, as shown in Figure 3, was determined to be crystal form I.

[0052] Example 5

[0053] 0.5 g of compound I prepared in Example 1 was placed in a 100 mL round-bottom flask. 20 mL of ethyl acetate was added to the active pharmaceutical ingredient powder. The mixture was heated and stirred in a water bath at 50 °C for 3 h, then filtered. The filtrate was allowed to stand for 7 days to allow the solvent to evaporate. The precipitated solid was filtered, washed, and dried to obtain a white crystalline solid with a yield of 51.8% and a purity of 99.51%. X-ray powder diffraction analysis confirmed that the white crystalline solid was crystal form I.

[0054] Example 6

[0055] 0.5 g of compound I prepared in Example 1 was placed in a 100 mL round-bottom flask. 15 mL of acetonitrile was added to the active pharmaceutical ingredient powder. The mixture was heated and stirred in a water bath at 50 °C for 3 h, then filtered. The filtrate was allowed to stand for 7 days to allow the solvent to evaporate. The precipitated solid was filtered, washed, and dried to obtain a white crystalline solid with a yield of 47.3% and a purity of 99.27%. X-ray powder diffraction analysis confirmed that the white crystalline solid was crystal form I.

[0056] Example 7

[0057] 0.5 g of compound I prepared in Example 1 was placed in a 100 ml round-bottom flask. 30 mL of tetrahydrofuran was added to the active pharmaceutical ingredient powder. The mixture was heated and stirred in a water bath at 50 °C for 3 h, then filtered. The filtrate was allowed to stand for 7 days to allow the solvent to evaporate. The precipitated solid was filtered, washed, and dried to obtain a white crystalline solid with a yield of 43.1% and a purity of 99.46%. X-ray powder diffraction analysis confirmed that the white crystalline solid was crystal form I.

[0058] Preparation Example 1

[0059] Preparation of 20% of compound I in crystalline or amorphous aqueous suspension:

[0060] Water and propylene glycol were added to a mixing tank, followed by the additives SOPROPHOR SC and NS-500LQ. The mixture was thoroughly stirred until the additives were completely dissolved. Then, compound I and magnesium aluminum silicate were added. The material was sheared and homogenized using a high-speed shear mill, and then transferred to a horizontal nano-sand mill for circulating grinding. The particle size was monitored using a laser particle size analyzer. When the particle size reached D... 90The material can be discharged when the particle size is below 800 nm. Then, 3% xanthan gum stock solution and BIT are added for viscosity adjustment. After the operation, a 20% aqueous suspension of compound I is obtained. The formulation product has good flowability. The components are shown in Table 2 below:

[0061] Table 2: Components of Aqueous Suspension Concentrates

[0062] Test Example 1

[0063] Thermal storage experiment of water suspension:

[0064] The aqueous suspension sample prepared in Example 1 was sealed in ampoules and stored in an oven at 54°C for 14 days. The fluidity of the suspension was then observed, water separation was detected, and the water separation rate, suspension rate, and particle size were calculated. The data were compared with those before heat storage. The analytical testing methods are as follows:

[0065] Water separation rate determination: Inject 10 mL of sample into a graduated ampoule, seal with an alcohol burner, and store at (54±2)℃ for 14 days. Observe the total height of the sample and the height of the transparent water layer, and calculate the water separation rate according to the formula: Water separation rate = Height of transparent water layer / Total height of sample × 100%.

[0066] Suspension rate determination: 1 gram of the test sample suspension was diluted with standard hard water to prepare 2000 grams of drug solution. The solution was allowed to stand in a graduated cylinder for 30 minutes at room temperature. The content of the active ingredient in the bottom tenth of the suspension was measured, and its suspension rate was calculated.

[0067] Particle size determination: 0.5 mL of suspension sample was added to the sample cell of a laser particle size analyzer, ultrasonically dispersed for 1 minute, and then measured. Each treatment was repeated 3 times. The experimental results are shown in Table 3 below.

[0068] Table 3: Results of thermal storage experiments on 20% Compound I crystal form I and amorphous aqueous suspensions

[0069] As can be seen from the data in Table 3, under the same conditions, after 14 days of heat storage, the aqueous suspension of compound I showed lower water separation, higher fluidity, higher suspension rate, smaller particle size and no significant change compared to the amorphous form. This indicates that the suspension of crystalline form I of compound I has excellent heat storage stability.

[0070] Test Example 2

[0071] Aqueous suspension activity test of Tetranychus cinnabarinus:

[0072] Take 0.1 g of the 20% aqueous suspension of compound I (crystal form I or amorphous form) prepared in Preparation Example 1 and add it to a 10 mL volumetric flask. Add purified water to make up to 10 mL to obtain a 1000 mg / L solution. Take 0.625 g of the 1000 mg / L solution and add purified water to make up to 100 mL to obtain a 6.25 mg / L solution. Dilute with water to a lower required test concentration solution.

[0073] Remove one true leaf from bean seedlings that have grown to two true leaves. Inoculate with Tetranychus carmineus and assess the initial mite population. Spray the entire plant with a handheld sprayer. Repeat each treatment three times (approximately 0.5g of the preparation). Observe the plants in a constant-temperature observation room after treatment. After 72 hours, assess the number of live mites and calculate the mortality rate. The experiment was repeated three times, with 35-100 Tetranychus carmineus inoculated each time.

[0074] Mortality rate % = (Number of inoculated worms - Number of live worms after treatment) ÷ Number of inoculated worms × 100%.

[0075] Table 4: Results of the activity test of aqueous suspension of Tetranychus cinnabarinus.

[0076] As can be seen from the test results in Table 4, the 20% Compound I crystal form I aqueous suspension exhibits excellent activity against Tetranychus cinnabarinus, and its acaricidal activity is significantly improved compared to the aqueous suspension prepared from the amorphous active ingredient.

[0077] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A crystalline form I of a pyridine-imidazolium compound, said pyridine-imidazolium compound having the structure shown in Formula I: The crystal form I exhibits at least three of the following diffraction peaks given as 2θ values ​​in its X-ray powder diffraction pattern: 6.02, 6.20, 6.28, 6.50, 10.06, 11.76, 14.86, 17.02, 18.48, 18.62, 19.56, 19.68, 21.38, 24.88, 28.58, 29.76, 31.72, 32.80, 37.64, 38.06, 38.48, 41.26, 44.20, 44.50, and 44.98, with each 2θ value having an error range within ±0.2°.

2. The crystal form I according to claim 1, characterized in that, The crystal form I exhibits at least three of the following diffraction peaks given as 2θ values ​​in the X-ray powder diffraction pattern: 6.02, 6.28, 10.06, 11.76, 14.86, 17.02, 18.48, 18.62, 19.68, 21.38, 28.58, 29.76, and 44.20, with each 2θ value having an error range within ±0.2°.

3. The crystal form I according to claim 2, characterized in that, The crystal form I shows at least three of the following diffraction peaks given in 2θ values ​​in the X-ray powder diffraction pattern: 6.02, 6.28, 10.06, 18.48, 18.62, 21.38, and 44.20, with the error range of each 2θ value within ±0.2°.

4. The crystal form I according to claim 3, characterized in that, The crystal form I has an X-ray powder diffraction pattern as shown in Figure 1, Figure 2 or Figure 3.

5. A method for preparing crystal form I of a pyridine-imidazole compound, the method comprising the following steps: Compound I was added to solvent A, heated and stirred until dissolved, then filtered. The filtrate was allowed to stand to allow the solvent to evaporate. The precipitated solid was then filtered, washed, and dried to obtain a white crystalline solid. The pyridine-imidazolium compound has the structure shown in Formula I: Solvent A is selected from one or more of ethyl acetate, tetrahydrofuran, and acetonitrile.

6. The preparation method according to claim 5, characterized in that, The mass-to-volume ratio of compound I to solvent A is 1:20-60 (g / mL); And / or, the pyridine-imidazole compound in crystal form I is crystal form I as described in any one of claims 1-4.

7. An insecticidal and acaricidal composition comprising crystal form I as described in any one of claims 1-4 or crystal form I prepared by the preparation method described in claim 5 or 6, wherein the weight percentage of crystal form I is 1%-50%.

8. The insecticidal and acaricidal composition according to claim 7, characterized in that, The insecticidal and acaricidal composition further includes component B, which has a weight percentage of 1%-50%; the insecticidal and acaricidal composition also includes agriculturally or forestry-acceptable adjuvants or carriers.

9. The insecticidal and acaricidal composition according to claim 8, characterized in that, Component B is selected from the following substances: butylated urea, triazotin, tricyclic tin, phenylbutylated tin, propargite, trichlorfon, bromonitrile dimethyl dimethoate, acetamiprid, acetamiprid, fipronil, pyridaben, pyrazopyr, flupyrazole, butenpyram, isoxaflutole, cyproconazole, flenazopyr, aflonana, fluoxazolamide, oxazolylflupronil, sarolaner, lotelanana, sarolaner, flusulfanilamide, amphetamine, avermectin, emamectin benzoate. Spinosad, ethyl spinosad, tetradifon, thiamethoxam, etoxazole, flufenoxam, flufenoxuron, flupentiofenox, Sulfiflumin, flufenoxuron, benzyladenine, pyridaben, pyrimethanil, pyridaben, pyridaben, pyridaben, acetamiprid, etoxazole, cyprodinil, diflubenzuron, bifenazate, pyrimethanil, flometoquin, flufenoxuron, spirodiclofen, spirotetramat, or spirodiclofen.

10. The insecticidal and acaricidal composition according to any one of claims 7-9, characterized in that, The formulation of the insecticidal and acaricidal composition is selected from suspension concentrates, soluble granules, suspension seed dressing agents, granules, microparticles, or water-dispersible granules. Preferably, the suspension concentrate is selected from water-based suspension concentrates, wherein the water-based suspension concentrate contains crystal form I at a weight percentage between 1% and 50%, and further includes a dispersant at a weight percentage between 1% and 20%, a wetting agent at a weight percentage between 1% and 20%, a thickener at a weight percentage between 0.01% and 10%, a preservative at a weight percentage between 0.01% and 10%, an antifreeze agent at a weight percentage between 1% and 20%, and the balance being water.

11. The use of crystal form I as described in any one of claims 1-4, crystal form I prepared by the preparation method described in claim 5 or 6, or the insecticidal and acaricidal composition as described in any one of claims 7-10 in the control of insect pests and mites.

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