链状4,4'-联吡啶桥联钴配位聚合物的晶体结构与量子化学计算

Crystal structure and quantum chemical calculation of chain coordination polymer with cobalt(Ⅱ) and 4,4'-bipyridine

六水合硝酸钴与4,4'-联吡啶在乙醇与水的混合溶液中反应,合成了一维链状配位聚合物{[Co(4,4'-bipy)(NO_3)_2(H_2O)_2]·2H_2O}_n,经IR、元素分析和X-射线单晶衍射表征结构。配合物晶体属正交晶系,空间群Pccn,晶体学参数:a=1.1760(2)nm,b=1.9537(3)nm,c=0.74195(12)nm,V=1.7047(5)nm^3,Z=4,Dc=1.602Mg·m^(-3),μ(MoKα)=1.065 mm^(-1),F(000)=844,R_1=0.0365,wR_2=0.0930。晶体结构分析表明,配合物中心Co离子为六配位畸变八面体构型,通过4,4'-联吡啶N原子桥联成一维无限链状,经分子间氢键作用进一步扩展成三维超分子。利用G03W程序在LANL2DZ基组对配合物中[Co(C_5N_1H_4)(NO_3)(H_2O)]结构单元进行理论计算研究。

A novel 1D chain coordination polymer {[Co（4,4＇-bipy）（NO3）2（HzO）2]＇2H20}n was synthesized by the reaction of Co（NO3）2.6H20 with 4,4＇-bipyridine in ethanol-water mixture, and was characterized by elemental analysis, IR and single crystal X-ray diffraction. The crystal belongs to orthorhombic system, space group Pccn with the cell parameters： a = 1.1760（2） nm, b = 1.9537（3） nm, c = 0.74195（12） nm, V= 1.7047（5） nm3, Z = 4, Dc = 1.602 Mg＇m-3, p（MoKa） = 1.065 mm-l, F（000） = 844, Rl = 0.0365 and wR2 = 0.0930. The structural analysis shows a distorted octahedral configuration with six-coordination for the cetral cobalt ion, which is bridged by the nitrogen atoms of 4,4＇-bipyridine, forming a 1D infinite chain, and further extended into a 3D supramolecular structure by intermolecular hydrogen-bonding interactions. A theoretical investigation of [Co（CsNIH4）（NO3）（H20）] was carried out at LANL2DZ level with Guassian 03W program. CCDC： 942634.