Coordination chemistry of new sulfur-containing ligands. 20. Preparation, characterization, and crystal and molecular structure of a severely distorted copper(II) N2S2 complex: [N,N'-tetramethylenebis(methyl 2-amino-1-cyclopentenedithiocarboxylato)]copper(II)
Coordination chemistry of new sulfur-containing ligands. 20. Preparation, characterization, and crystal and molecular structure of a severely distorted copper(II) N2S2 complex: [N,N'-tetramethylenebis(methyl 2-amino-1-cyclopentenedithiocarboxylato)]copper(II)
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新型含硫配体的配位化学。
DOI：
10.1021/ic50221a043
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发表时间：
1981
影响因子：
4.6
通讯作者：
J. Dorfman
中科院分区：
文献类型：
--
作者：
R. Bereman;G. Shields;J. Bordner;J. Dorfman
X 10 - 4cm-1，g|| A0 = 2.140，A0= 55.9 × 10 - 4cm-1，g 0 = 2.066）表明该配合物比具有三个碳骨架的类似配合物甚至从平面配合物向四面体配合物更扭曲。因此，在一系列密切相关的CuN 2S 2配合物的失真和光谱性质之间的确切关系的研究是可能的。标题化合物的晶体和分子结构在室温下通过单晶X-射线衍射研究解决。晶体属中心对称单斜晶系，空间群Cl/c，a= 16.782（8）A，B= 8.626（4）A，c= 14.621（8）A，λ = 105.83（4），V= 2036（1）× 3，d^（d^）= 1.51（1.50）g cm-3，分子量462.2，Z= 4.对于所有908个可观察到的反射，试验结构的全矩阵最小二乘细化导致RF= 4.6%的差异指数和“拟合优度”= 1.71。分子是单体，分离良好，位于C2轴上。铜-硫距离为2.221（2）A，铜-氮距离为1.955（4）A。五元螯合环中的键距表明了令人惊讶的离域量。由铜和两个配位硫原子定义的平面与由铜和两个氮原子定义的平面相交，形成57.1的二面角（90对于假四面体N2 S2内部配位球是理想的）。作为这些CuN 2和CuS 2平面的扭曲角的函数的光谱特性的变化进行了讨论。此外，可能的相关性，I型铜（II）中心的金属酶。
X 10" 4 cm" 1, g||= 2.140, A0= 55.9 X 10" 4 cm" 1, g0= 2.066) suggest that this complex is even more distorted from a planar complex toward a tetrahedral one than the similar complex with a three carbon backbone. A study of the exact relationships between distortion and spectral properties in a closely related series of CuN2S2 complexes is thus possible. The crystal and molecular structure of the title compound was solved at room temperature by a single-crystal X-ray diffraction study. The complex crystallizes in the centrosymmetric monoclinic space group Cl/c with a= 16.782 (8) Á, b= 8.626 (4) A, c= 14.621 (8) A, ß= 105.83 (4), V= 2036 (1) Á3, d^¡(d^)= 1.51 (1.50) g cm" 3 for mol wt 462.2 and Z= 4. Full-matrix least-squares refinementof the trial structure resulted in discrepancy indices of RF= 4.6% and “goodness-of-fit"= 1.71 for all 908 observable reflections. The molecules are monomeric, are well separated, and lie on a C2 axis. The copper-sulfur distance is 2.221 (2) A, and the copper-nitrogen distance is 1.955 (4) A. Bond distances in the five-membered chelate ring indicate a surprising amount of delocalization. The plane defined by the copper and two liganded sulfur atoms intersects the plane defined by the copper and two nitrogen atoms, forming a dihedral angle of 57.1 (90 would be ideal for a pseudotetrahedral N2S2 inner coordination sphere). The variation of spectral properties as a function of twist angle of these CuN2 and CuS2 planes is discussed. In addition, the possible relevance to type I copper (II) centers in metalloenzymes is presented.