三(邻甲基苄基)锡和二(间氟苄基)锡硫代水杨酸酯配合物的合成、结构及性质

doi:10.11944/j.issn.1000-0518.2017.02.160183

摘要/Abstract

摘要：

合成了三(邻甲基苄基)锡硫代水杨酸酯配合物(1)和一维链状二(间氟苄基)锡硫代水杨酸酯配合物(2),经元素分析、IR、NMR、X射线衍射等技术手段表征了其结构。配合物1属三斜晶系,空间群Pī,晶体学参数a=1.00221(5) nm,b=1.48934(8) nm,c=1.71789(9) nm,α=78.3120(10)°,β=85.6560(10)°,γ=80.2580(10)°,V=2.4725(2) nm³,Z=2,D_c=1.371 g/cm³,μ(MoKα)=10.91 cm^-1,F(000)=1040,R₁=0.0439,wR₂=0.1119。配合物2属单斜晶系,空间群为P2₁/n,晶体学参数:a=1.17827(5) nm,b=2.11945(9) nm,c=1.55970(7) nm,β=93.4510(10)°,V=3.8880(3) nm³,Z=4,D_c=1.671 g/cm³,μ(MoKα)=14.53 cm^-1,F(000)=1936,R₁=0.0323,wR₂= 0.0927。配合物1中锡原子呈四配位畸变四面体构型,配合物2中锡原子呈五配位畸变三角双锥构型。配合物1和2分别在152和195 ℃下稳定,电化学性质不可逆,对人体癌细胞Colo205、HepG2、MCF-7、Hela和NCI-H460具有体外抗癌活性,配合物2的抗癌活性远大于配合物1。

关键词: 三(邻甲基苄基)锡硫代水杨酸酯, 二(间氟苄基)锡硫代水杨酸酯, 合成, 结构, 抗癌活性

Abstract:

Tris(o-methylbenzyl)tin thiosalicylate(1) and di(m-fluorobenzyl)tin thiosalicylate(2) have been synthesized. Crystal structures of the complexes were determined by X-ray diffraction. Crystal 1 belongs to the triclinic space group Pī with a=1.00221(5) nm, b=1.48934(8) nm, c=1.71789(9) nm, α=78.3120(10)°, β=85.6560(10)°, γ=80.2580(10)°, V=2.4725(2) nm³, Z=2, D_c=1.371 g/cm³, μ(MoKα)=10.91 cm^-1, F(000)=1040, R₁=0.0439, wR₂=0.1119. Crystal 2 belongs to the monoclinic space group P2₁/n with a=1.17827(5) nm,b=2.11945(9) nm,c=1.55970(7) nm,β=93.4510(10)°,V=3.8880(3) nm³,Z=4,D_c=1.671 g/cm³,μ(MoKα)=14.53 cm^-1,F(000)=1936,R₁=0.0323,wR₂= 0.0927. The tin atoms in complexes 1 and 2 have four coordinates in a distorted tetrahedral configuration and five coordinates in a distorted trigonal bipyramidal configuration, respectively. Further more, the thermal stability and electrochemical and anticancer activity of the complexes were tested. The results show that complexes 1 and 2 are stable below 152 ℃ and below 195 ℃, respectively, and show irreversible redox process. Complexes 1 and 2 display in vitro anti-tumor activity against five human tumor cell lines Colo205, Hep G2, MCF-7, Hela and NCI-H460, and the anti-tumor activity of complex 2 is higher than that of complex 1.

Key words: tris(o-methylbenzyl)tin thiosalicylate, di(m-fluorobenzyl)tin thiosalicylate, crystal structure, in vitro anticancer activity

张复兴, 邝代治, 李璇捷, 冯泳兰, 王剑秋, 庾江喜, 蒋伍玖, 朱小明. 三(邻甲基苄基)锡和二(间氟苄基)锡硫代水杨酸酯配合物的合成、结构及性质[J]. 应用化学, 2017, 34(2): 163-171.

ZHANG Fuxing, KUANG Daizhi, LI Xuanjie, FENG Yonglan, WANG Jianqiu, YU Jiangxi, JIANG Wujiu, ZHU Xiaoming. Synthesis, Structures and Properties of Tris(o-methylbenzyl)tin Thiosalicylate and Di(m-fluorobenzyl)tin Thiosalicylate[J]. Chinese Journal of Applied Chemistry, 2017, 34(2): 163-171.

参考文献

[1]	Munoz-Flores B M,Santillán R,Farfán N,et al. Synthesis, X-ray Diffraction Analysis and Nonlinear Optical Properties of Hexacoordinated Organotin Compounds Derived from Schiff Bases[J]. J Organomet Chem,2014,769:64-71.
[2]	Jr C E C,Roner M R J. Organotin Polymers as Anticancer and Antiviral agents[J]. J Organomet Chem,2014,751:67-82.
[3]	Chandrasekhar V,Thirumoorthi R,Metre R K,et al.Steric Control in the Reactions of 3-Pyrazolecarboxylic Acid with Diorganotin Dichlorides[J]. J Organomet Chem,2011,696(2):600-606.
[4]	YIN Handong,WANG Chuanhua,HONG Min,et al.Synthesis, Properties and Crystal Structure of Diorganotin(Ⅳ) Compound with Schiff Base Ligand Pyruvic Acid Isonicotinyl Hydrazone [Ph2Sn(C9H7N3O3)·(H2O)]2[J]. Chinese J Appl Chem,2007,24(10):1124-1127(in Chinese). 尹汉东,王传华,洪敏,等. 丙酮酸异烟酰腙合锡(Ⅳ)配合物[Ph2Sn(C9H7N3O3)·(H2O)]2的合成、性质和晶体结构[J]. 应用化学,2007,24(10):1124-1127.
[5]	Sedaghat T,Aminian M,Bruno G,et al.Binuclear Organotin(Ⅳ) Complexes with Adipic Dihydrazones:Synthesis, Spectral Characterization, Crystal Structures and Antibacterial Activity[J]. J Organomet Chem,2013,737:26-31.
[6]	Hong M,Yin H D,Zhang X Y,et al.Di- and Tri-organotin(Ⅳ) Complexes with 2-Hydroxy-1-Naphthaldehyde 5-Chloro-2-Hydroxybenzoylhydrazone:Synthesis, Characterization and in Vitro Antitumor Activities[J]. J Organomet Chem,2013,724:23-31.
[7]	YU Jiangxi,FENG Yonglan,KUANG Daizhi,et al.Microwave Assisted Synthesis, Structural Characterization, Thermal Stability and in Vitro Anticancer Activity of Tricyclohexyltin 8-Quinolinoxide[J]. Chinese J Appl Chem,2014,31(8):937-942(in Chinese). 庾江喜,冯泳兰,邝代治,等. 三环己基锡8-羟基喹啉配合物的微波辅助合成、结构表征、热稳定性和体外抗癌活性[J]. 应用化学,2014,31(8):937-942.
[8]	Carraher J C E,Roner M R. Organotin Polymers as Anticancer and Antiviral Agents[J]. J Organomet Chem,2014,751: 67-82.
[9]	Sun M L,Ruan B F,Tian Y P,et al.Synthesis, Crystal Structures, Electrochemical Studies and Anti-Tumor Activities of Three Polynuclear Organotin(Ⅳ) Carboxylates Containing Ferrocenyl Moiety[J]. J Organomet Chem,2011,696:3180-3185.
[10]	ZHANG Fuxing,KUANG Daizhi,FENG Yonglan,et al.Synthesis, Structure and Antitumor Activity of Tri(o-bromobenzyl)tin Dithiotetrahydropyrrolocarbamate[J]. Chinese J Appl Chem,2014,31(3):285-289(in Chinese). 张复兴,邝代治,冯泳兰,等. 三(o-溴苄基)锡吡咯烷基二硫代甲酸酯的合成、结构及体外抗癌活性[J]. 应用化学,2014,31(3):285-289.
[11]	Li D M,Hu R H,Wu Z,et al.Synthesis, Structures, and Photophysical Properties of two Organostannoxanes from a Novel Acrylic Acid Derived from Phenothiazine[J]. Eur J Inorg Chem,2009,2009(18):2664-2672.
[12]	XIE Qinglan,HE Xilin,HE Shuiji,et al.Synthesis Characterization and Pesticidal Activities of Bis(Trialkyltin) Dicarboxylates[J]. Acta Chem Sin,1999,57:210-218(in Chinese). 谢庆兰,贺烯林,贺水济,等. 双(三烃基锡)二元羧酸酯的合成、结构和农药活性普筛[J]. 化学学报,1999,57:210-218.
[13]	ZHANG Fuxing,WANG Jianqiu,KUANG Daizhi,et al.Synthesis, Crystal Structure and Quantum Chemistry of the Tricyclohexyltin 2-Amino-6-chloro Benzoate[J]. Chinese J Inorg Chem,2012,28(9):1890-1894(in Chinese). 张复兴,王剑秋,邝代治,等. 三环已基锡-2-氨基-6-氯苯甲酸酯配合物的合成结构及量子化学研究[J]. 无机化学学报,2012,28(9):1890-1894.
[14]	Sedaghat T,Aminian M,Rudbari H A,et al.Dinuclear Organotin(Ⅳ) Complexes with Bis-acyl-hydrazones Containing Flexible Linker:Synthesis, Spectroscopic Investigation and Crystal Structure of Dimethyl- and Diphenyltin(Ⅳ) Complexes with Succinic Dihydrazones[J]. J Organomet Chem,2014,754:26-31.
[15]	ZHANG Fuxing,WANG Jianqiu,KUANG Daizhi,et al.Microwave Assisted Solid-State Synthesis, Crystal Structure and Quantum Chemistry of the Tri(o-chlorobenzyl)tin Cinnamate[J]. Chinese J Inorg Chem,2011,27(6):1111-1115(in Chinese). 张复兴,王剑秋,邝代治,等. 微波固相合成三(邻氯苄基)锡肉桂酸酯及其结构与量子化学研究[J]. 无机化学学报,2011,27(6):1111-1115.
[16]	Mahmudov K T, Guedes M F C,Kopylovich M N, et al. Di- and Tri-organotin(Ⅳ) Complexes of Arylhydrazones of Methylene Active Compounds and their Antiproliferative Activity[J]. J Organomet Chem,2014,760:67-73.
[17]	KUANG Daizhi,FENG Yonglan,YU Jiangxi,et al.Microwave Assisted Solid-state Synthesis, Crystal Structure, Properties of the Coordination Polymer Constructed from Tricyclohexyltin Hydroxide and o-Ferrocenylcarbonyl Benzoic Acid[J]. Chem J Chinses Univ,2014,35(8):1629-1634(in Chinese). 邝代治,冯永兰,庾江喜,等. 三环己基锡邻(二茂铁甲酰基)苯甲酸酯配位聚合物的微波固相合成、晶体结构及性能[J]. 高等学校化学学报,2014,35(8):1629-1634.
[18]	ZHANG Fuxing,KUANG Daizhi,WANG Jianqiu,et al.Synthesis and Crystal Structure of the Tri(o-methylbenzyl)tin Chloride and the Bis(p-methylbenzyl)tin Dichloride[J]. Chinese J Inorg Chem,2006,22(7):1246-1250(in Chinese). 张复兴,邝代治,王剑秋,等. 三(邻甲基苄基)氯化锡和二(对甲基苄基)二氯化锡的合成和晶体结构[J]. 无机化学学报,2006,22(7):1246-1250.
[19]	George M S. SHELXTL-97:Program for Crystal Structure Analysis.Göttingen[M]. University of Göttingen,1997.
[20]	YU Jiangxi,KUANG Daizhi,YIN Dulin,et al.Synthesis, Crystal Structure and Electrochemical Properties of the One-dimensional Chain Tri(n-butyl)tin 2,4-Dichloro-phenoxy Acetate[J]. Chinese J Inorg Chem,2010,26(8):1507-1510(in Chinese). 庾江喜,邝代治,尹笃林,等. 一维链状三正丁基锡2,4-二氯苯氧乙酸酯的合成、结构和电化学性质研究[J]. 无机化学学报,2010,26(8):1507-1510.
[21]	ZHANG Fuxing,KUANG Daizhi,FENG Yonglan,et al.Synthesis, Structure and Properties of Tricyclohexyltin L-Mandeliate[J]. Chinese J Appl Chem,2015,32(10):1120-1126(in Chinese). 张复兴,邝代治,冯泳兰,等. 三环已基锡L-扁桃酸酯配合物的合成、结构及性质[J]. 应用化学,2015,32(10):1120-1126.
[22]	ZHANG Fuxing,KUANG Daizhi,FENG Yonglan,et al.Synthesis, Structure and Antitumor Activity of Dis(o-bromobenzyl)tin Bis(dithiomethylcarbamate) and Dis(o-chlorobenzy)tin Bis(pyrrolidine dithiocarbamate)[J]. Chinese J Inorg Chem,2014,30(10):2367-2374(in Chinese). 张复兴,邝代治,冯泳兰,等. 二(o-溴苄基)锡双(二乙基二硫代氨基甲酸)酯和二(o-氯苄基)锡双(吡咯啶二硫代氨基甲酸)酯的合成、结构及体外抗癌活性研究[J]. 无机化学学报,2014,30(10):2367-2374.