【摘要】 标题两个化合物是在反应体系（NH4）3VS4／CuX／PPh3／NEt4X（X=Br，Ⅰ）中采用低温固相反应方法得到的，单晶X射线结构分析表明：VS4（CuPPh3）5Br2（Ⅰ）和VS4－（CuPPh3）5I2（Ⅱ）是同构的，其中晶体（Ⅰ）属于单斜晶系，空间群P211／c,Mr=19682，a=20.215（7），b=15．691（4），c=27.345（9）A，β=95.29（3）°，V=8637.0A3，Z=4，Dc=1．51g／cm3，F（000）=3968，μ（MoKa）=24．6cm-1，R=0.078。晶体（Ⅱ）亦属于单斜晶系，Mr=2062．2，空间群P21／c,a=20.1613（2），b=15．9718（2），c=27.7427（3）A，β=96.07（1）°，V=8883．4A3，Z=4，Dc=1．54g／cm3，F（000）=4112，μ（MoKa）=22．0cm－1，R=0．068。簇合物（Ⅰ）和（Ⅱ）的簇芯结构可描述为共面的2个开口的扭曲立方烷，在这两个簇合物中，V原子仍保持反应起始物[VS4]3-中的四面体配位，5个CU原子呈近似的四方锥排列，V原子基本上处于Cu5四方锥底面的中心。其中1个Cu原子为平面三角形配位，另外4个Cu原子为严重畸变的四面体配位。更多还原

【Abstract】 The title two compounds have been obtained in the reaction system (NH4 )3 VS4 /CuX /PPh3 /NEt4X(X=Br, I) by the method of solid state reaction at low heating temperature. Single crystal X-ray structural analyses show that the structures of VS4 (CuPPh3 ),Br2 (I) and VS4-(CuPPh3)4I2(Ⅱ) are the same. Crystal (I) is monoclinic space group P21/c with Mr= 1968. 2,a = 20. 215(7),b= 15. 691 (4),c= 27. 345(9) A,β=95. 29(3)°,V=8637. 0 A 3,Z= 4,Dc=1. 51 g/cm3,F(000) = 3968,μ(MoKa) = 24. 6 cm-1,R=0. 078. Crystal (Ⅱ) is also monoclinicspace group P21/c with Mr= 2062. 2, a= 20. 1613 (2),b= 15. 9718 (2),c= 27. 7427 (3) A, β=96. 07 (1 )°,V= 8883. 4 A3,Z=4,Dc= 1. 54 g/cm3,F(000) = 4112, μ(MoKa) = 22. 0 cm-1,R=0. 068. The core of clusters (Ⅰ) and (Ⅱ ) can be described as an open double distorted cubanestructure joined by a common face. In the clusters (Ⅰ) and (Ⅱ ), V atom has retained its initialtetrahedral coordination geometry of the reaction material [VS4]3. Five copper atoms form approximately a rectangular pyramid with the V atom nearly located at the center of the basal planeof the Cu5 rectangular pyramid. One Cu atom has trigonal planar coordination and the other fourCu atoms have distorted tetrahedral coordination.更多还原