过硫代碳酸配体［CS4］2-生成的新方法［Me4N］n［Cu(CS4)］n(I)和［Me4N］4［Cu4(CS4)4］(Ⅱ)的合成与晶体结构

用硒酚铜簇合物和硫酚铜簇合物Me4N]2Cu4(EPh)6](E=Se和S）与CS2及少量S反应，分别获得了以过硫代碳酸根CS4]^2-为配体的Me4N]nCu(CS4)]n(I)和Me4N]4Cu4(CS4)4](Ⅱ）。并用X射线单晶衍射法测定了它们的晶体结构。I为二维层状聚合物，Ⅱ为四核铜簇阴离子化合物。并对CS4]^2-形成的机理作了讨论。

A New Way to Formation of Perthiocarbonate Ligand Synthesis and Crystal Structures of ［Me4N］n［Cu(CS4)］n(Ⅰ)and ［Me4N］4［Cu4(CS4)4］(Ⅱ)

The solutions of tetranuclear copper cluster anionic complexes ［Me4N］2［Cu4(SePh)6］ or ［Me4N］2［Cu4(SPh)6］ in DMF or CH3CN reacted with CS2 in the presence of a small amount of S. From the resulting solutions brown-black block-shaped crystals Ⅰ or brown-red block-shaped crystals Ⅱ were formed, respectively. Crystal data: (Ⅰ) orthorhombic, space group Pbca, a=1.138 5(4) nm, b=1.668 3(4) nm, c=1.092 1(2) nm, V=2.074 2(9) nm3. μ=2.846 mm-1, F(000)=1 136 e, Dc=1.777 g/cm3, for Z=8, R=0.054 4 for 1 821 observed reflections; (Ⅱ) tetragonal, space group P421c, a=1.395 2(2) nm, b=1.395 2(2) nm, c=1.135 0(2) nm, V=2.209 4(6) nm3. μ=2.677 mm-1, F(000)=1 136e, Dc=1.671 g/cm3, for Z=8, R=0.064 5 for 1 114 observed reflections.The X-ray crystal structure determination indicated that the molecule of the complex Ⅰ consists of a polymeric anion ［Cu2(CS4)2］2-n and cations ［Me4N］+. In the polymeric anion, the repeated unit is a dinuclear copper complex ［Cu2(CS4)2］2-, which links to four surrounding aggregations through sulfur bridges to form a two-dimensional layer structure. The cations ［Me4N］+ locate between the layers. The molecule of complex Ⅱ consists of a tetranuclear copper cluster anion with four perthiocarbonate ligands ［Cu4(CS4)4］4- and four cations ［Me4N］+. The four copper atoms form a tetrahedron. One of the sulfur atoms in each CS2-4 ligand forms the sulfur bridge with two Cu atoms while the other is coordinated to only one copper.