高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (5): 717.

• 研究论文 • 上一篇    下一篇

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

汤卡罗, 金祥林, 龙耀玲, 崔澎, 唐有祺   

  1. 北京大学物理化学研究所, 北京 100871
  • 收稿日期:1999-11-30 出版日期:2001-05-24 发布日期:2001-05-24
  • 通讯作者: 金祥林(1940年出生),男,教授,从事X射线单晶结构分析研究.
  • 基金资助:

    国家自然科学基金(批准号:29733080和29873001)资助

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)

TANG Ka-Luo, JIN Xiang-Lin, LONG Yao-Ling, CUI Peng, TANG You-Qi   

  1. Institute of Physical Chemistry, Peking University, Beijing 100871, China
  • Received:1999-11-30 Online:2001-05-24 Published:2001-05-24

摘要: 用硒酚铜簇合物和硫酚铜簇合物[Me4N]2[Cu4(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]n[Cu(CS4)]n(Ⅱ)和[Me4N]4[Cu4(CS4)4](2-).并用X射线单晶衍射法测定了它们的晶体结构.为二维层状聚合物,为四核铜簇阴离子化合物.并对[CS4]2-形成的机理作了讨论.

关键词: 过硫代碳酸, 四核铜簇合物, 二维层状聚合物, 晶体结构

Abstract: The solutions of tetranuclear copper cluster anionic complexes [Me4N]2[Cu4(SePh)6] or [Me4N]2[Cu4(SPh)6] in DMFor CH3CNreacted 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=1.1385(4) nm, b=16683 (4) nm, c=10921(2) nm, V=20742(9) nm3. μ=2846 mm-1, F (000)=1136 e, Dc=1777 g/cm3, for Z=8, R=00544 for 1821 observed reflections; (Ⅱ) tetragonal, space group P421c, a=13952(2) nm, b=13952(2) nm, c=11350(2) nm, V=22094(6) nm3. μ=2677 mm-1, F (000)=1136e, Dc=1671 g/cm3, for Z=8, R=00645 for 1114 observed reflections.The X-ray crystal structure determination indicated that the molecule of the complex Ⅰ consists of a polymeric anion [Cu2(CS4)2]n2- 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.

Key words: Perthiocarbonate, Tetranuclear copper cluster anion, Two dimensional layer polymer, Crystal structure

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