二[1,2-二硫代(3,5-二硫杂-4-硫酮)戊烯]铜和锌络合物的四丁基胺盐的晶体结构

1,2-二硫代烯基(1)和1,2-二硫代苯基(Ⅱ)类型的金属络合物的研究,已有很多报道。但Ⅰ和Ⅱ与Zn的络合物的晶体结构至今未见报道。Gray等人发现在[N(C_4H_8)_4]_2[M′(MNT)_2]络合物的X射线粉末图中,Co,Pt,Ni络合物的衍射花样完全相同,但Zn络合物的确有明显的不同。Billig等人在[N(C_2H_5)_4]_2[M″(MNT)_2](M″=Cu,Ni,Zn)络合物的X射线粉末花样中也观察到同样的现象。他们认为Zn络合物为四面体的构型,但未测定其结构。近来,Lindqvist又推出一种1,2-二硫代(3,5-二硫杂-7-硫酮)戊烯基(Ⅲ)新的配位体。为了解Cu,Zn与Ⅲ形成络合物的特征,本文测定了标题络合物的晶体结构。

CRYSTAL STRUCTURES OF TETRABUTYLAMMONIUM BIS(ISOTRITHIONEDITHIOLATO) COPPER (Ⅱ) AND ZINC (Ⅱ)

The crystal structures of the title compounds have been determined from threedimensional intensity measured on a R3m/E four circle diffractometer. The crystallographic data are listed in Table 1. The structure of [N(C_4H_9)_4]_2[Cu(S_5C_3)_2] was solved by trial and error using isomophous [N(C_4H_9)_4]_2[Pd(S_5C_3)_2] crystal data. The structure of [N(C_4H_9)_4]_2[Zn(S_5C_3)_2] was solved by direct method using SHELXTL program system. The H atom coordinates were calculated geometrically. The refinement of coordinates and anisotropic thermal parameters was performed by “blocked cascade” least squares to R=0.044 for Cu(II) compound and R=0.057 for Zn(II) compound calculated on the basis of 2424 and 1219 independent reflections respectively. All the numerical calculations were carried out on a Eclipse/S_(140) computer with programs of R3m/E system....