TRIGONAL PRISMATIC COORDINATION . CRYSTAL AND MOLECULAR STRUCTURE OF TRIS(CIS-1,2-DIPHENYLETHENE-1,2-DITHIOLATO(RHENIUM
TRIGONAL PRISMATIC COORDINATION . CRYSTAL AND MOLECULAR STRUCTURE OF TRIS(CIS-1,2-DIPHENYLETHENE-1,2-DITHIOLATO(RHENIUM
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DOI：
10.1021/ic50037a018
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发表时间：
1966-01-01
影响因子：
4.6
通讯作者：
IBERS, JA
中科院分区：
文献类型：
--
作者：
EISENBER.R;IBERS, JA
用标准胶片技术收集的三维单晶X射线数据确定了三（顺式-1，2-二苯基乙炔-1，2-二硫代）钒（ViSgCgiCeHsGs）的晶体和分子结构。该结构已被细化的最小二乘法的常规R因子为0.077为1516非零反射。晶体属单斜晶系，空间群C2/c，晶胞尺寸a = 19.25，B = 11.31，c = 18.01 A; δ = 106.3; V = 3763 A~3。实验测得的密度为1.36 ± 0.04 g/cm~3，与计算值1.37 g/cm~3相当吻合。晶体学要求V ^CjICjHs ^s具有双重对称轴，钒占据空间群的4（e）特殊位置。六个硫给体原子以三角棱柱配位围绕钒酸盐。因此，XASgCgiCeHjkk是含有第一行过渡金属的分子六配位络合物中三角棱柱配位的第一个例子。棱镜的尺寸与第二和第三行金属的络合物惊人地相似。配体内和配体间的平均SS距离近似相等（分别为3.058和3.064），但棱镜绕三重轴有轻微的畸变。详细比较了X/SgCgCeH2/、Re（S2O2（O6）2）3和Mo（S2C2H2）3的分子结构，这加强了先前提出的配体间键合作为三角棱柱配位中的稳定因素的概念。
The crystal and molecular structure of tris (czs-l, 2-diphenylcthene-l, 2-dithiolato) vanadium, ViSgCgiCeHsGs, has been deter-mined from three-dimensional single-crystal X-ray data collected by standard film techniques. The structure has been re-fined by least-squares methods to a conventional R factor of 0.077 for 1516 nonzero reflections. The neutral complex crystal-lizes in space group C2/c of the monoclinic system with a cell of dimensions a= 19.25, b= 11.31, c= 18.01 A; 8= 106.3; V= 3763 A3. An experimental density of 1.36±0.04 g/cm3 is in good agreement with a calculated value of 1.37 g/cm3 for four molecules in the unit cell (Z= 4). V^ CjICjHs^ s is crystallographically required to possess a twofold symmetry axis with vanadium occupying the 4 (e) special positions of the space group. The six sulfur donor atoms surround the van-adium in a trigonal-prismatic coordination. As such, XASgCgiCeHjkk is the first example of trigonal-prismatic coordination in a molecular six-coordinate complex containing a first-row transition metal. The dimensions of the prism are strikingly similar to those found for complexes of second-and third-row metals. Average intra-and interligand SS distances arc approximately equal (3.058 and 3.064 A, respectively), but there is a slight distortion of theprism about the threefold axis. A detailed comparison of the molecular structures of X/SgCgiCeHj//, Re (S202 (06^) 2) 3, and Mo (S2C2H2) 3 is presented which reinforces the previously suggested notion of interligand bonding as a stabilizing factor in trigonal-prismatic coordination.