4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O的合成及晶体结构

标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。

SYNTHESIS AND CRYSTAL STRUCTURE OF 4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O

The title compound has been synthesized by the reaction of (NH_4)_2WS_4 and CuCl_2·2H_2O in pyridine solution, 4CuCl(C_5H_5N)_4] ·W_(10)O_(32)]·2(C_5H_5N)·3H_2O is triclinic, space group P1, a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)°. V=2.907(3) nm, z=1. D_m=2.56 gcm~(-3). The structure was solved by Patterson method and Fourier methods. The final R is 0.046. The result indicates that the crystal is composed of W_(10)O_(32)~(4-), CuCl(C_5H_5N)_4]~+, C_5H_5N and H_2O. The structure of W_(10)O_(32)~(4-) is shown in Fig.1. The W atom is coordinated by six O atoms of octahedra, which united by edges and corner. The structure of CuCl(C_5H_5N)_4]~+ isshown in Fig.2. The Cu atom is coordinated by one Cl and four N atoms that form slightly deformed pyramid. This kind of CuCl(C_5H_5N)_4]~+ cation has not been reported before. C_5H_5N and H_2O molecules are distributed in the interstices of the packing of the ions.