The electrostatic nature of aryl-bromine-halide synthons:: The role of aryl-bromine-halide synthons in the crystal structures of the trans-bis(2-bromopyridine)dihalocopper(II) and trans-bis(3-bromopyridine)dihalocopper(II) complexes
The electrostatic nature of aryl-bromine-halide synthons:: The role of aryl-bromine-halide synthons in the crystal structures of the trans-bis(2-bromopyridine)dihalocopper(II) and trans-bis(3-bromopyridine)dihalocopper(II) complexes
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DOI：
10.1021/cg060154b
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发表时间：
2006-08-02
影响因子：
3.8
通讯作者：
Twamley, Brendan
中科院分区：
文献类型：
--
作者：
Awwadi, Firas F.;Willett, Roger D.;Twamley, Brendan
本文研究了C-Br中心点中心点中心点X电子在Cu（nbp）（2）X-2（nbp）= n-溴吡啶（n = 2和3）结构中的作用。比较这些电子在这些结构和先前发表的（nBP）（2）CuX 4和（nBP）X结构中的作用（nBP = n-溴吡啶鎓阳离子; X = Br-或Cl-; n = 2、3或4）表明静电效应，溴吡啶鎓阳离子上的正电荷和卤素阴离子上的负电荷，对C-Br中心点的强度和方向性起主要作用。数据表明，与Cu（nbp）（2）X-2化合物相比，（nBP）（2）CuX-4和（nBP）X盐中的C-Br中心点中心点这些Cu（nbp）（2）X-2配合物的超分子组装主要由非传统的C-Br中心点X配位离子和Cu中心点X半配位键组成。在Cu（3bp）（2）X-2中，溴-卤化物的距离几乎等于它们的货车德瓦尔斯半径之和（r（vdW）），但比r（vdW）之和小0.24埃。Cu（3bp）（2）Cl-2和Cu（2bp）（2）Cl-2的C-Br中心点中心点X角接近线性，范围分别为158.15（8）度至167.90（8）度。Cu（2bp）（2）X-2单元形成基于C-Br中心点中心点X配体的链状结构。这些链通过C-H中心点、中心点、中心点X和π-π堆积相互作用形成三维结构。而Cu（3bp）（2）X-2化合物的链状结构是基于Cu，X半配位键。这些链通过C-Br中心点、中心点、中心点X介子相互作用形成三维结构。
The role of C-Br center dot center dot center dot X synthons in the structures of Cu(nbp)(2)X-2 (nbp) = n-bromopyridine; n = 2 and 3) are investigated. A comparison of the role of these synthons in these and in the previously published (nBP)(2)CuX4 and (nBP) X structures (nBP = n-bromopyridinium cations; X = Br- or Cl-; n = 2, 3, or 4) indicate that electrostatic effects, the positive charge on the bromopyridinium cation and the negative charge on the halide anion, play a major role in the strength and directionality of C- Br center dot center dot center dot X synthons. The data indicates that the C- Br center dot center dot center dot X synthons are stronger in the (nBP)(2)CuX4 and (nBP) X salts compared with the Cu(nbp)(2)X-2 compounds. The supramolecular assembly of these Cu(nbp)(2)X-2 complexes is dominated by nontraditional C- Br center dot center dot center dot X synthons and Cu center dot center dot center dot X semicoordinate bonds. The bromine-halide distances are almost equal to the sum of their van der Waals radii (r(vdW)) in Cu(3bp)(2)X-2 but less than the sum of the r(vdW) by similar to 0.24 angstrom in Cu(2bp)(2)X-2. The C- Br center dot center dot center dot X angles are close to linear, ranging from 158.15(8)degrees to 167.90(8)degrees for Cu(3bp)(2)Cl-2 and Cu(2bp)(2)Cl-2 respectively. The Cu(2bp)(2)X-2 units form chain structures based on the C-Br center dot center dot center dot X synthons. These chains interact via C-H center dot center dot center dot X and pi-pi stacking to form the three-dimensional structure. In contrast, the chain structures in Cu(3bp)(2)X-2 compounds are based on the Cu,,, X semicoordinate bond. These chains interact via C-Br center dot center dot center dot X synthons to form the three-dimensional structure.