N,N＇-二(3-氨丙基)草酰胺合铜的双核Cu(Ⅱ)-Zn(Ⅱ)配合物的合成和结构

Synthesis and Structure of Binuclear Cu(Ⅱ)-Zn(Ⅱ)Complexes with N,N'-Bis(3-aminopropyl)oxamido Copper(Ⅱ)

合成和表征了三个异核配合物:[Cu(oxpn)Zn(bpy)_2](ClO_4)_2·1/2H_2O(1),[Cu(oxpn)Zn-(phen)_2](ClO_4)_2·2H_2O(2),[Cu(oxpn)Zn(NO_2-phen)_2](ClO_4)_2·2H_2O(3)[bpy=2,2′-联吡啶、phen=1,10-菲咯啉、NO_2-phen=5-硝基-1,10-菲咯啉、oxpn=N,N′-二(3-氨丙基)草酰胺阴离子].2的晶体属单斜晶系,P2/n 空间群,晶胞参数:a=1.5061(3),b=1.2924(3),c=2.2802(3)nm,β=108.42(2)°,V=4.1869 nm^3,Z=4,D_m=1.409g/cm^3,μ=12.812cm^(-1),F(000)=1812,最终的偏离因子 R=0.093,R_w=0.099.结构分析证实,配合物具有扩充的草酰胺桥联结构,Cu(Ⅱ)及 Zn(Ⅱ)的配位环境分别为平面四边形和畸变的八面体构型,阳离子的对称性近似为 C_(2v).此外,本文还指派了配合物的电子光谱,并对 EPR、有效磁矩等数据进行了讨论.

From the planar monomeric fragment Cu(oxpn),where oxpn is N,N'-bis(3-aminopropyl) oxamido,we have synthesized three complexes,namely [Cu(oxpn)Zn-(bpy)_2] (ClO_4)_2·1/2H_2O(1,bpy=2,2'-bipyridyl),[Cu (oxpn)Zn(phen)_2] (ClO_4)_2·2H_2O(2,phen=1,10-phenanthroline),[Cu(oxpn)Zn(NO_2-phen)_2] (ClO_4)_2·2H_2O(3,NO_2-phen=5-nitro-1,10-phenanthroline).The crystal structure of 2 has beendetermined.Crystal data for 2:monoclinic,space group P2/n,a=1.5061(3),b=1.2924(3),c=2.2802(3)nm,β=108.42(2)°,V=4.1869 nm^3,Z=4,D_m=1.409 g/cm^3,μ=12.812 cm^(-1),F(000)=1812.The final R and R_w values are 0.093 and 0.099 respectively.It is shown that complexes have extended oxamidobridged structure and consist ofCu(Ⅱ) in a square planar environment and Zn(Ⅱ) in a distorted octahedralenvironment.The cation symmetry is closed to C_2v.In addition,the absorption bandshave been assigned to be d-d transitions and charge transitions.The EPR spectra andeffective magnetic moments of these complexes are also discussed.