Structural studies of metal dithiocarbamates. II. The crystal and molecular structure of copper diethyldithiocarbamate
Structural studies of metal dithiocarbamates. II. The crystal and molecular structure of copper diethyldithiocarbamate
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DOI：
10.1107/s0365110x65004619
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发表时间：
1965-12
期刊：
影响因子：
--
通讯作者：
M. Bonamico;G. Dessy;A. Mugnoli;A. Vaciago;L. Zambonelli
中科院分区：
文献类型：
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作者：
M. Bonamico;G. Dessy;A. Mugnoli;A. Vaciago;L. Zambonelli
用三维方法测定了铜（II）双（N， N-二乙基二硫代氨基甲酸酯），[(C2Hs) zNCSz] zCu在室温下的晶体结构，并采用微分傅立叶合成法进行了各向异性细化（最终R值为0-081）。单斜胞内有4个公式单元，a= 9.907, b= 10.627, e= 16.591 a, 8= 113 52′，空间群为P21/c。每一对中心对称相关的铜原子共用硫原子，从而形成一个双分子单位。铜的四个硫原子在2.297和2.339 a的距离上呈扭曲的四边形-锥体配位，第五个顶端硫原子在2.851 a的距离上。铜与重原子的最短分子间接触是在3.78 a处与碳原子的接触，这意味着氢原子位于距铜2.86 a的第六个八面体位置。配体分子是平面的（明显与末端的CH3基团分开），硫碳键的长度在1.708 ~ 1-736之间。，两个C (sp2)- n (sp2)(-)（+）键长分别为1.33 A和1.35 A。正如之前的红外工作所预期的那样，…-$2 C= NR2是二乙基二硫代氨基甲酸铜结构中的一个重要规范形式。本系列的第一篇论文（Bonamico, Dessy, Maria-ni, Vaciago & Zambonelli, 1965）给出了研究金属二硫代氨基甲酸酯结构的一般原因。本实验室研究的第二种化合物是铜（II）双（N， N-二乙基二硫代氨基甲酸酯）：HsCz SS C2H5\/ a/\/N—C Cu C—N/\/\//\H5C2 SS C2Hs，化学键顺序为常规顺序。第一个确定铜盐结构的是Peyronel （Pignedoli & Peyronel, 1962；以及其中引用的先前参考文献），他发表了二正丙基衍生物的二维结构分析。几个研究小组（Shugam & Shkol'nikova, 1958; Va-ciag0, Gramaccioli & Pullia, 1960; Bally, 1963）也发表了关于铜（II） bis （N， N-二乙基二硫代氨基甲酸盐）的初步研究成果。然而，仍然缺乏铜的配位的详细几何图以及键长和键角的精确数据。在这个阶段，另一个有趣的问题是需要解释铜和锌晶体参数的惊人相似性
The crystal structure of copper (II) bis (N, N-diethyldithiocarbamate),[(C2Hs) zNCSz] zCu, at room temp-erature, has been determined by three-dimensional meth~ d~, including anisotropic refinement by dif-ferential Fourier synthesis (final R value, 0-081). There are four formula units in the monoclinic cell, a= 9.907, b= 10.627, e= 16.591 A, 8= 113 52', with space group P21/c. Each pair of centrosymmetric-ally related copper atoms share sulphur atoms, thus forming a bimolecular unit. Copper has a distorted tetragonal-pyramidal coordination of four sulphur atoms, at a distance ranging between 2.297 and 2.339 A, and a fifth apical sulphur atom at 2.851 A. The shortest intermolecular copper contact to a heavy atom is to a carbon atom at 3.78 A, which implies a hydrogen atom occupying the sixth octahedral position at 2.86 A from the copper. The ligand molecules are planar (obviously apart from the terminal CH3 groups), the sulphur-carbon bond lengths range from 1.708 to 1-736.~, and the two C (sp2)-N (sp2)(-)(+) bonds are 1.33 and 1.35 A long. As expected from previous infrared work,..-$2 C= NR2 is an important canonical form in the structure of copper diethyldithiocarbamate.Introduction The first paper of this series (Bonamico, Dessy, Maria-ni, Vaciago & Zambonelli, 1965) gave the general reasons for the investigation of the structure of metal dithiocarbamates. The second compound investigated in our labora-tory was copper (II) bis (N, N-diethyldithiocarbamate): HsCz SS C2H5\/'a/\/N--C Cu C--N/\/\//\H5C2 SS C2Hs with the bond orders written in the conventional way. The first structural determination of a copper salt was that of Peyronel (Pignedoli & Peyronel, 1962; and previous references quoted therein), who published a two-dimensional structure analysis of the di-n-propyl derivative. Preliminary work was also published on copper (II) bis (N, N-diethyldithiocarbamate) by several research groups (Shugam & Shkol'nikova, 1958; Va-ciag0, Gramaccioli & Pullia, 1960; Bally, 1963). A detailed geometrical picture of the coordination of copper and accurate data on bond lengths and angles, however, were still lacking. A further interesting point at this stage was the need for explanation of the striking similarity in the crystal parameters of copper and zinc