摘要
分别合成了 [Co(3, 3-tri)(men)Cl][ZnCl4]、[Co(3, 3-tri)(cmen)Cl][ZnCl4] (3, 3-tri = N-(3-胺基丙基)-1, 3-丙二胺,men = N-甲基乙二胺,cmen = 1, 2-二胺基-丙烷) 2体系的部分配合物异构体,用单晶 X-射线衍射分析方法解析了2异构体的晶体结构。其中 [Co(3, 3-tri)(men)Cl][ZnCl4] 体系的一异构体Ⅰ的化学简式为 CoCl(C9H27N5)ZnCl4,晶体属正交晶系,空间群 Pca21,a = 16.788(2),b = 7.964(1),c = 14.416(2) 牛琕 =1927.3(4) ?,Dc = 1.747 g/cm3,Z = 4,F(000) = 1032,Mr = 506.91,R = 0.0352,wR =0.0935;[Co(3, 3-tri)(cmen)Cl]2+ 体系的一异构体Ⅱ的化学简式为 CoCl(C9H27N5)ZnCl4稨2O, 晶体属三斜晶系,空间群 P ,a = 9.511(3), b = 9.972(3),c = 11.694(3) 牛琣 = 68.367(5),b = 85.196(6),?= 86.580(5),V = 1026.9(5)?3,Dc = 1.698 g/cm3,Z = 2,F(000) = 536,Mr = 524.92,R = 0.0494,wR = 0.1180。两异构体中 Co3+ 为六配位,晶胞中对映体比例均为1:1。在配合物异构体Ⅰ和Ⅱ中,三元胺以经式排布,三元胺配体(3, 3-tri)仲胺上的氢相对于Cl分别处于顺位(syn-)和反位(anti-);二元胺配体氮(或邻位碳)取代的胺基氮原子(N*)与三元胺配体中的仲氮原子分别处于对位(trans(N*))和邻位(cis(N*))。
Some geometric isomers of two new systems, [Co(3, 3-tri)(men)Cl]2+ Ⅰ and [Co(3, 3-tri)(cmen)Cl]2+Ⅱ, have been synthesised by decomposing per-oxide complex (3, 3-tri = N-(3-aminopropyl)-1, 3-propanediamine; men = N-methylethylenediamine; cmen = 1, 2-diaminopropane). The crystal structures of two complexs have been determined by single-crystal X-ray diffraction. The crystals of isomer Ⅰ in the [Co(3, 3-tri)(men)Cl]2+ system belong to orthorhombic, space group Pca21 with a = 16.788(2), b = 7.964(1), c = 14.416(2) , V =1927.3(4) 3, Dc = 1.747 g/cm3, Z = 4, F(000) = 1032, R = 0.0352 and wR =0.0935. There are four complex cations which are enantiomers with a ratio of 1 : 1, and four [ZnCl4]2- anions in a unit cell; the crystals of isomer Ⅱ in the [Co(3, 3-tri)(cmen)Cl]2+ system belong to triclinic, space group P ?with a = 9.511(3), b = 9.972(3), c = 11.694(3) ? a = 68.367(5), b = 85.196(6), = 86.580(5), V = 1026.9(5) 3, Dc = 1.698 g/cm3, Z = 2, F(000) = 536, R = 0.0494 and wR = 0.1180. There are two complex cations which are also enantiomers with a ratio of 1 : 1, two [ZnCl4]2- anions and two latticed H2O molecules in a unit cell. In the complexes Ⅰ and Ⅱ, the arrangement of the triamine ligand is meridian, and the NH proton of triamine is syn- and anti- to Cl in the cation, respectively; the nitrogen(N) of substituted amine (or next to the substituted carbon) in the diamine ligand is trans(N) and cis(N) to the NH proton of triamine ligand.
基金
贵州省省长基金
贵州省科技基金(NO:003060)
贵州大学科技基金资助项目
