溶剂对磺胺甲基嘧啶溶剂化合物形成的影响

doi:10.11949/0438-1157.20190642

摘要/Abstract

摘要：

采用悬浮转化法对磺胺甲基嘧啶溶剂化合物在醇类、酯类和酰胺类等17种溶剂中进行了筛选研究，采用粉末 X 射线衍射、热重分析、扫描电镜和傅里叶红外光谱对磺胺甲基嘧啶溶剂化合物进行了表征，成功制备出磺胺甲基嘧啶与N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮溶剂化物和二甲基亚砜的4种溶剂化合物。热重结果表明它们均属于化学计量比为1∶1的溶剂化合物；扫描电镜分析发现在溶剂化合物形成过程中，晶体的形态由接近正方体的块状晶体变为片状与棒状晶体；傅里叶红外表征分析证实了溶剂化合物中溶剂与溶质分子形成分子间氢键。分析所用的17种溶剂的分子结构、氢键供体和受体能力等性质，确定了磺胺甲基嘧啶容易与氢键受体能力强的溶剂形成相应溶剂化合物。对比分析了晶体中分子的堆积效率，进一步证实了磺胺甲基嘧啶形成氢键溶剂化合物。根据磺胺甲基嘧啶和溶剂化合物的单晶结构，分析氢键溶剂化合物形成前后分子堆积、结构合成子和氢键网络的变化，磺胺甲基嘧啶晶型Ⅱ及其溶剂化合物的四种结构中均形成一维的椅子形氢键网络，对于三种溶剂化合物，除了磺胺甲基嘧啶分子间形成的氢键网络，磺胺甲基嘧啶分子氨基中另一个氢原子与溶剂分子的氧原子相连形成分子间N—H…O氢键。结果表明氢键在溶质与溶剂间的超分子自组装过程中起决定作用，是影响溶剂化合物形成的关键因素。

关键词: 磺胺甲基嘧啶, 溶剂性质, 氢键受体能力, 分子间氢键

Abstract:

The solvent compounds of sulfamethylpyrimidine were screened in 17 kinds of solvents, such as alcohols, esters and amides, and the sulfamerazine solvates were investigated by powder X-ray diffraction, thermal gravimetric analysis, scanning electron microscopy and Fourier transform infrared spectroscopy. The results showed that sulfamerazine can form four solvates with N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide respectively. TGA results showed that they all belong to the type of 1∶1 stoichiometric solvates. SEM results indicated that the morphology of the crystals changed significantly after the formation of the solvates, the morphology of the crystal changed from block shape to sheet and rod crystal. FTIR characterization analysis confirmed that the solvent and the solute molecules formed intermolecular hydrogen bonds in the solvates. The physicochemical properties of the used solvents for the screening were analyzed, and the results showed that the corresponding solvates were easy to form in the solvents with strong hydrogen bond acceptor ability. The packing efficiency of molecules in crystals further confirmed that sulfamerazine form hydrogen bond solvates. The changes of molecular packing, structure synthons and hydrogen bond network before and after the formation of solvates were determined according to the single crystal structures of compounds. Sulfamerazine form Ⅱ and its solvates formed a one-dimensional leader hydrogen bond network. For three solvates, in addition to the hydrogen bond network formed between the molecules of sulfamerazine, another hydrogen atom in the amino group of sulfamerazine was bonded to the oxygen atom of the solvent molecule to form an intermolecular N—H…O hydrogen bond.The results showed that the hydrogen bond played a decisive role in the supramolecular self-assembly process between the solute and the solvent, then affected the formation of solvates.

Key words: sulfamerazine, solvent properties, hydrogen bond acceptor ability, intermolecular hydrogen bond

中图分类号:

TQ 028.8

张霞, 周玲, 尹秋响. 溶剂对磺胺甲基嘧啶溶剂化合物形成的影响[J]. 化工学报, 2020, 71(2): 680-687.

Xia ZHANG, Ling ZHOU, Qiuxiang YIN. Effects of solvent on formation of sulfamerazine solvates[J]. CIESC Journal, 2020, 71(2): 680-687.

图/表 10

图1 磺胺甲基嘧啶在筛选溶剂中所得产品的粉末XRD谱图

Fig.1 XPRD patterns of products obtained from screening solvents

图2 磺胺甲基嘧啶溶剂化合物的TGA&DSC图

Fig.2 TGA and DSC curves of SMZ solvates

图3 磺胺甲基嘧啶及溶剂化合物的SEM图

Fig.3 SEM images of SMZ and SMZ solvates

图4 不同SMZ溶剂化合物的FTIR图

Fig.4 FTIR of different SMZ solvate

表1 溶剂性质及筛选所得到的晶型

Table 1 Properties of used solvents and obtained forms

溶剂	α	β	π*	SMZ晶型
N-甲基吡咯烷酮	00	77	92	溶剂化合物
N,N-二甲基乙酰胺	00	76	88	溶剂化合物
N,N-二甲基甲酰胺	00	69	88	溶剂化合物
二甲基亚砜	00	76	100	溶剂化合物
甲酰胺	71	48	97	晶型Ⅱ
乙腈	19	40	75	晶型Ⅱ
甲醇	98	66	60	晶型Ⅱ
乙醇	86	75	54	晶型Ⅱ
正丙醇	84	90	52	晶型Ⅱ
异丙醇	76	84	48	晶型Ⅱ
正丁醇	84	84	47	晶型Ⅱ
仲丁醇	79	84	40	晶型Ⅱ
甲酸乙酯	00	36	61	晶型Ⅱ
乙酸甲酯	00	42	60	晶型Ⅱ
乙酸乙酯	00	45	55	晶型Ⅱ
乙酸丙酯	00	40	—	晶型Ⅱ
丙酮	08	43	71	晶型Ⅱ

图5 研究中使用的一些溶剂的分子结构

Fig.5 Molecular structures of some solvents used for solvates investigated herein

表2 磺胺甲基嘧啶晶型Ⅱ和三种溶剂化合物的单晶结构数据

Table 2 Crystallographic data for SMZ form Ⅱ and SMZ solvates (SMZ-DMF, SMZ-DMA and SMZ-NMP)

参数	SMZ form Ⅱ^①	SMZ-DMF^②(1∶1)	SMZ-DMA^③(1∶1)	SMZ-DMA(1∶1)	SMZ-NMP(1∶1)
分子式	C₁₁H₁₂N₄O₂S	C₁₄H₁₉N₅O₃S	C₁₅H₂₁N₅O₃S	C₁₅H₂₁N₅O₃S	C₁₆H₂₁N₅O₃S
分子量	264.3	337.41	351.44	351.43	363.44
晶系	正交	三斜	三斜	三斜	三斜
空间群	Pn2₁a	$P 1 ˉ$	$P 1 ˉ$	$P 1 ˉ$	$P 1 ˉ$
a/?	14.474(2)	9.774(2)	7.6792(15)	7.8727(16)	9.516(2)
b/?	21.953(2)	12.556(3)	8.3101(17)	8.3117(17)	13.137(3)
c/?	8.203(1)	14.659(3)	15.125(3)	15.506(3)	15.146(4)
α/(°)	90	76.58(3)	93.13(3)	95.01(3)	105.224(8)
β/(°)	90	77.57(3)	101.81(3)	102.38(3)	94.743(4)
γ/(°)	90	86.18(3)	104.77(3)	105.83(3)	92.175(7)
晶胞体积/?³	2606.48	1708.6(6)	907.7(4)	941.916	1817.22
Z	8	1	2	2	4
Z'	2	0.5	1	1	2
R1/%	4.7	7.25	6.41	6.71	4.03
GOF	n/a	n/a	n/a	1.023	1.092

表2 磺胺甲基嘧啶晶型Ⅱ和三种溶剂化合物的单晶结构数据

Table 2 Crystallographic data for SMZ form Ⅱ and SMZ solvates (SMZ-DMF, SMZ-DMA and SMZ-NMP)

参数	SMZ form Ⅱ^①	SMZ-DMF^②(1∶1)	SMZ-DMA^③(1∶1)	SMZ-DMA(1∶1)	SMZ-NMP(1∶1)
分子式	C₁₁H₁₂N₄O₂S	C₁₄H₁₉N₅O₃S	C₁₅H₂₁N₅O₃S	C₁₅H₂₁N₅O₃S	C₁₆H₂₁N₅O₃S
分子量	264.3	337.41	351.44	351.43	363.44
晶系	正交	三斜	三斜	三斜	三斜
空间群	Pn2₁a	$P 1 ˉ$	$P 1 ˉ$	$P 1 ˉ$	$P 1 ˉ$
a/?	14.474(2)	9.774(2)	7.6792(15)	7.8727(16)	9.516(2)
b/?	21.953(2)	12.556(3)	8.3101(17)	8.3117(17)	13.137(3)
c/?	8.203(1)	14.659(3)	15.125(3)	15.506(3)	15.146(4)
α/(°)	90	76.58(3)	93.13(3)	95.01(3)	105.224(8)
β/(°)	90	77.57(3)	101.81(3)	102.38(3)	94.743(4)
γ/(°)	90	86.18(3)	104.77(3)	105.83(3)	92.175(7)
晶胞体积/?³	2606.48	1708.6(6)	907.7(4)	941.916	1817.22
Z	8	1	2	2	4
Z'	2	0.5	1	1	2
R1/%	4.7	7.25	6.41	6.71	4.03
GOF	n/a	n/a	n/a	1.023	1.092

图6 SMZ晶型Ⅱ和它们相应的溶剂化合物的堆积系数

Fig.6 Packing coefficients of SMZ form Ⅱ and its solvates

图7 不同晶体结构中分子堆积图

Fig.7 Crystal packing in different crystal structures

表3 磺胺甲基嘧啶晶型Ⅱ和三种溶剂化合物中氢键数据

Table 3 Hydrogen bonding data for SMZ form Ⅱ and SMZ solvates (SMZ-DMF, SMZ-DMA and SMZ-NMP)

化合物	SMZ分子间N—H…N氢键/?	SMZ分子间N—H…O氢键/?	SMZ分子与溶剂分子间N—H…O氢键/?
SMZ form Ⅱ	2.899, 2.947	3.056	—
SMZ-DMF	2.896, 2.911	3.032	2.875, 2.832
SMZ-DMA	2.897	3.02	2.829
SMZ-NMP	2.918	3.047	2.851

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