草酸根桥联双核配合物Cd2(phen)2ox(NO3)2·(H2O)2的合成、结构及态密度分析

摘要

通过草酸钾(k2ox·H2O)、硝酸镉[Cd(NO3)2·4H2O]和1,10-邻菲咯啉(phen)在甲醇·水溶液中的反应合成了一种双核镉配合物[Cd2(phen)2ox(NO3)2(H2O)2],其结构经单晶X射线衍射表征.配合物属三斜晶系,P(1)空间群,晶胞参数:a=0.67629(14)nm,b=1.0051(2)nm,c=1.0527(2)nm,α=109.19(3)°,β=92.12(3)°,γ=93.48(3)°,γ=0.6733(2)nm3,Z=1,D=2.055 g/cm3,F(000)=410,μ=1.660mm-1,R=0.0445,wR=0.0877.配合物为草酸根桥联的双核镉配合物,且草酸根C-C键中点为配合物的倒反中心,镉与ox2-,phen,NO3-和水配位.运用晶体场理论计算了其态密度,结果表明NO3-和phen对配合物的性质有重要影响.%A dinuclear Cd ( Ⅱ ) complex [Cd2 (phen)2ox( NO3 )2 (H2 O)2]was synthesized by mixing potassium oxalate ( K2ox · H2O ), cadmium nitrate [Cd ( NO3 ) 2 · 4H2O]and 1,10-phenanthroline ( phen ) in methanol-water solution. The structure was characterized by X-ray single-crystal diffraction analysis. It belongs to triclinic system, P1 space group with α =0. 67629(14) nm, b = 1. 0051 (2) nm, c = 1. 0527(2) nm, α = 109. 19(3)°, β=92. 12(3)°, γ=93.48(3)°, V=0.6733(2) nm3, Z=l, D=2.055 g/cm3, F(000) = 410,μ = 1. 660 mm-1, R =0. 0445, wR =0. 0877. The analytical results indicate that it is an oxalate-bridged dinuclear Cd( Ⅱ ) complex, the midpoint of carbon-carbon bond of oxalate is the center of inversion for the complex, Cd( Ⅱ ) cation coordinates with ox2- , phen, NO3- and H2O. The crystal field theory was used to calculate density of state(DOS) for the complex. Analysis results show that NO3- and phen have important influence on the properties of the complex.