Department of Chemistry, Guru Nanak Dev University, Amritsar - 143 005, India.
Department of Microbiology, Guru Nanak Dev University, Amritsar-143 005, India.
Dalton Trans. 2017 Jan 24;46(4):1324-1339. doi: 10.1039/c6dt04103e.
An equimolar reaction of copper(i) iodide with N-ethyl-imidazolidine-2-thione (l-Et) in acetonitrile formed black prismatic crystals over a period of three weeks. The X-ray structure determination of black crystals revealed that the thio-ligand l-Et has transformed into a new thio-ligand, 1-ethyl-3-(1-ethyl-4,5-dihydro-1H-imidazol-2-yl)imidazolidine-2-thione (l-NEt), through C-S rupture/C-N bond formation which was coordinated in the unusual 2D polymer, {(Cu(κ-N,S-l-NEt))·(CuI)·(CuI)}1. An ESR spectrum supported the presence of divalent Cu in the polymer. In contrast, reaction of copper(i) iodide with N-phenyl-imidazolidine-2-thione (l-Ph) in 1 : 1 molar ratio yielded a polymer, [-Cu(μ-I)Cu(μ-S-l-Ph)Cu-]2, with alternate CuI and CuS cores. Further, a series of reactions of copper(i) halides with N-substituted imidazolidine-2-thiones, namely, l-R in 1 : 2 metal to ligand molar ratio (M : L) in acetonitrile have yielded different type of complexes: trigonal planar {CuX(κ-S-l-R), R, X : Et, I, 4; Me, I, 5; Bu, I,6; Me, Br,7; Bu, Br, 8; Me, Cl, 9; Pr, Cl, 10; Ph, Cl, 11}, dinuclear [CuBr(μ-S-l-Ph)(κ-S-l-Ph)] 12, tetranuclear, [CuI(μ-I)(μ-S-l-Ph)(κ-S-l-Ph)] 3 and hexanuclear [CuCl(μ-S-l-Bu)] 13. All these complexes have been characterized using analytical data, IR and proton NMR spectroscopy, ESI-mass studies and single crystal X-ray crystallography. The antimicrobial activity of these complexes has been investigated against Gram positive bacteria, namely, Staphylococcus aureus (MTCC740), methicillin resistant Staphylococcus aureus (MRSA), Gram negative bacteria, Klebsiella pneumoniae (MTCC109), Salmonella typhimurium (MTCC741) and Candida albicans (MTCC227)- a yeast. It is significant to add that among various complexes tested for cytotoxicity toward living cells, 4, 5, 8, 9 and 10 complexes were toxic, while complex 12 was non-toxic.
碘化亚铜与 N-乙基-2-硫代咪唑烷（l-Et）在乙腈中发生等摩尔反应，经过三周的时间形成黑色棱柱晶体。通过 X 射线结构测定，黑色晶体中的硫代配体 l-Et 通过 C-S 断裂/C-N 键形成，转化为一种新的硫代配体 1-乙基-3-(1-乙基-4,5-二氢-1H-咪唑-2-基)咪唑烷-2-硫酮（l-NEt），形成了一种不寻常的 2D 聚合物，{(Cu(κ-N,S-l-NEt))·(CuI)·(CuI)}1。ESR 光谱支持聚合物中存在二价 Cu。相比之下，碘化亚铜与 N-苯基-2-硫代咪唑烷（l-Ph）以 1:1 摩尔比反应，生成具有交替的 CuI 和 CuS 核的聚合物[-Cu(μ-I)Cu(μ-S-l-Ph)Cu-]2。此外，一系列铜（I）卤化物与 N-取代的 2-硫代咪唑烷的反应，即 l-R 在 1:2 金属与配体摩尔比（M：L）在乙腈中，生成了不同类型的配合物：三角平面 {CuX(κ-S-l-R), R, X：Et, I, 4; Me, I, 5; Bu, I, 6; Me, Br, 7; Bu, Br, 8; Me, Cl, 9; Pr, Cl, 10; Ph, Cl, 11}，双核 [CuBr(μ-S-l-Ph)(κ-S-l-Ph)] 12，四核 [CuI(μ-I)(μ-S-l-Ph)(κ-S-l-Ph)] 3 和六核 [CuCl(μ-S-l-Bu)] 13。所有这些配合物均通过分析数据、IR 和质子 NMR 光谱、ESI-质谱研究和单晶 X 射线晶体学进行了表征。研究了这些配合物对革兰氏阳性菌（金黄色葡萄球菌（MTCC740）、耐甲氧西林金黄色葡萄球菌（MRSA））、革兰氏阴性菌（肺炎克雷伯菌（MTCC109）、鼠伤寒沙门氏菌（MTCC741））和白色念珠菌（酵母）的抗菌活性。值得注意的是，在所测试的各种对活细胞具有细胞毒性的复合物中，4、5、8、9 和 10 种复合物具有毒性，而复合物 12 则没有毒性。
