Structure of (1,10‐phenanthroline)bis(4‐toluenethiolato)zinc(II)
Structure of (1,10‐phenanthroline)bis(4‐toluenethiolato)zinc(II)
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(1,10-菲咯啉)双(4-甲苯硫醇)锌(II)的结构
DOI：
10.1107/s0567740880010898
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发表时间：
1980
期刊：
影响因子：
--
通讯作者：
G. Crosby
中科院分区：
文献类型：
--
作者：
T. Cremers;D. R. Bloomquist;R. Willett;G. Crosby
Zn(C12HsNz)(CTH7S)2), (Zn(phen)(4-tol- S)2)，单斜，P21/c, a = 10.009 (3), b = 20.12 (1), c = 12.140(4) a, t= 107.73(1)°，Pcalc = 1.403, Pobs = 1.396 Mg m -3, Z = 4；R = 0.058, R = 0.061。zn2 +中心金属离子的配位几何为畸变四面体，S-Zn-S键角为126.2°，N-Zn-N键角为78.7°。N-Zn-S键角范围为107 ~ 113°。介绍。锌与通式(Zn(SL)2(N-N)) （N-N =取代的1,10-菲罗啉或2,2'-联吡啶，SL =取代的苯乙醇）的配合物具有光谱上的兴趣（Truesdell, 1978; Koester, 1975）。Truesdell已经合成了大量这样的配合物（包括标题配合物），并注意到存在一个不寻常的，宽的，无结构的可见吸收带及其相应的发射。这些过渡是配合物所特有的，不存在于不配位的配体中。Truesdell将这种转变解释为本质上的配体间跨金属电荷转移。为了解释这种转变，Truesdell提出了一种基于金属C2v配位几何的分子轨道模型。这里报告的结构分析是为了检查中心金属原子周围的配位。从金属和配体的化学计量混合物的乙醇溶液中沉淀法制备了明亮的黄色(Zn（phen)(4-tol- S)2）块。将具有{010}、{010}、{011}和{0ii}面的小晶体（0.12 × 0.25 × 0.29 mm）安装在与测角仪主轴轴线共线的e轴上。类型hOl （l = 2n + 1）和0k0 （k = 2n + 1）的系统不存在唯一地定义了空间群P2~/e。强度数据采集在全自动Picker全圆衍射仪与zr滤波Mo - Ka辐射。采用0-20步扫描，扫描范围为1.8°，20步度-~和3.0 s步-1。在每次扫描前后分别进行15秒的背景测量。强度标准差计算为：oZ(Io) = TC + BC + (0.33) 210 2
Zn(C12HsNz)(CTH7S)2), (Zn(phen)(4-tol- S)2), monoclinic, P21/c , a = 10.009 (3), b = 20.12 (1), c = 12.140(4)A, t= 107.73(1) ° , Pcalc = 1.403, Pobs = 1.396 Mg m -3, Z = 4; R = 0.058, R w = 0.061. The coordination geometry of the Zn 2+ central metal ion is distorted tetrahedral with a S-Zn-S bond angle of 126.2 ° and a N-Zn-N bond angle of 78.7 °. The N-Zn-S bond angles range from 107 to 113 °. Introduction. Complexes of Zn with the general formula (Zn(SL)2(N-N )) (N-N = substituted 1,10- phenanthroline or 2,2'-bipyridine, SL = substituted benzenethiol) are of spectroscopic interest (Truesdell, 1978; Koester, 1975). Truesdell has synthesized a large number of these complexes (including the title complex) and noted the presence of an unusual, broad, struc- tureless visible absorption band and its corresponding emission. The transitions were unique to the complexes and not present in the uncoordinated ligands. The transition was interpreted by Truesdell as interligand transmetallic charge transfer in nature. To account for this transition, Truesdell then proposed a molecular- orbital model based on C2v coordination geometry of the metal. The structural analysis reported here was undertaken to examine the coordination around the central metal atom. Bright, yellow chunks of (Zn(phen)(4-tol- S)2) were prepared by precipitation from an ethanol solution of stoichiometric mixtures of the metal and ligands. A small crystal (0.12 × 0.25 × 0.29 mm) with {010}, {010}, {011}, and {0ii} faces developed was mounted with the e axis collinear with the spindle axis of the goniometer. Systematic absences of the types hOl (l = 2n + 1) and 0k0 (k = 2n + 1) uniquely defined the space group as P2~/e. Intensity data were collected on an automated Picker full-circle diffractometer with Zr-filtered Mo Ka radiation. A 0-20 step scan was used with scans of 1.8 °, 20 steps deg -~ and 3.0 s step -1. Background measurements of 15 s were made before and after each scan. The standard deviation in intensity was calculated by oZ(Io) = TC + BC + (0.33)21o 2