Crystal chemistry of the 4,4'-dimethyl-2,2'bipyridine/copper bromide system.
Crystal chemistry of the 4,4'-dimethyl-2,2'bipyridine/copper bromide system.
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DOI：
10.1021/ic010229v
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发表时间：
2001-07
影响因子：
4.6
通讯作者：
R. Willett;G. Pon;Callie Nagy
中科院分区：
文献类型：
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作者：
R. Willett;G. Pon;Callie Nagy
4,4'-二甲基-2,2-联吡啶（以下简称dmbp）与铜(I)和/或溴化铜（II）在多种条件下的反应分离出了10种不同的晶体材料。其中包括一种Cu(I)盐，[Cu(dmbp)(2)]Br（一种扭曲的四面体Cu物种和晶格Br（-）离子）；两个混合价Cu（I，II）化合物，[Cu(dmbp)(2)Br][CuBr(2)]（离散5配位Cu（II）和线性Cu(I)种）和Cu(dmbp)(2)BrCu(2)Br(3)（连接5配位Cu（II）和三角形平面Cu(I)种）；和7种Cu（II）化合物，（dmbp）CuBr(2)（堆叠平面单体），[(dmbp)CuBr(2)](2)（五坐标双桥二聚体），（dmbp）Cu(2)Br(4)（堆叠平面双桥二聚体），（dmbp）CuBr(2)(DMSO)（五坐标单体），[Cu(dmbp)(2)Br]OH。5(1)/(2)H(2)O和[Cu(dmbp)(2)Br]（Br/OH）。5(1)/(2)H(2)O（五个配位单体）和（dmbpH(2)）CuBr(4).H(2)O（畸变四面体单体）。报道了这些材料的晶体结构测定。它们结构化学中的一个共同线索是通过相邻分子物种的dmbp环的交叉发展而形成的超分子结构。交错作用导致了许多材料的层状结构。交叉dmbp环之间的距离在3.4-3.7 A之间。Cu(dmbp)(2)Br（+）由于Cu（dmbp）碎片平均面之间的二面角偏离90度而表现出特别大的四面体几何畸变。Cu(dmbp)(2)Br（+）阳离子具有扭曲的三角双锥体结构，Br（-）离子位于赤道位置。Cu(dmbp)(2)Br（+）中Cu-Br键的长度与两个dmbp配体平面间二面角的变化有关。单dmbp配合物在Cu（II）的配位几何上表现出较大的变化，包括扭曲的三角双锥体和增强的方形平面4 + 1和4 + 2配位。
The reaction of 4,4'-dimethyl-2,2-bipyridine (henceforth dmbp) with copper(I) and/or copper(II) bromide under a wide variety of conditions has led to the isolation of 10 different crystalline materials. These include one Cu(I) salt, [Cu(dmbp)(2)]Br (a distorted tetrahedral Cu species and a lattice Br(-) ion); two mixed valence Cu(I,II) compounds, [Cu(dmbp)(2)Br][CuBr(2)] (discrete 5-coordinated Cu(II) and linear Cu(I) species) and Cu(dmbp)(2)BrCu(2)Br(3) (linked 5-coordinate Cu(II) and trigonal planar Cu(I) species); and seven Cu(II) compounds, (dmbp)CuBr(2) (stacked planar monomers), [(dmbp)CuBr(2)](2)(five coordinate bibridged dimers), (dmbp)Cu(2)Br(4) (stacked planar bibridged dimers), (dmbp)CuBr(2)(DMSO) (five coordinate monomers), [Cu(dmbp)(2)Br]OH.5(1)/(2)H(2)O and [Cu(dmbp)(2)Br](Br/OH).5(1)/(2)H(2)O (five coordinate monomers), and (dmbpH(2))CuBr(4).H(2)O (distorted tetrahedral monomers). The crystal structure determinations of these materials are reported. A common thread in their structural chemistry is the supramolecular architecture developed through interdigitation of the dmbp rings on neighboring molecular species. The interdigitation leads to layer structures in many of the materials. The distances between the interdigitated dmbp rings are in the range 3.4-3.7 A. The Cu(dmbp)(2)Br(+) species exhibits an exceptionally large distortion from tetrahedral geometry due to deviation of the dihedral angle between the mean planes of the Cu(dmbp) fragments from 90 degrees. The Cu(dmbp)(2)Br(+) cations have distorted trigonal bipyramidal geometry, the Br(-) ion occupying an equatorial position. The length of the Cu-Br bond in the Cu(dmbp)(2)Br(+) species is correlated with the change in dihedral angle between the planes of the two dmbp ligands. The mono-dmbp complexes show a greater variation in coordination geometry for the Cu(II) species, including distorted trigonal bipyramidal and augmented square planar 4 + 1 and 4 + 2 coordination.