化学学报 ›› 1996, Vol. 54 ›› Issue (3): 276-280. 上一篇    下一篇

研究论文

新型二维七核簇合物[WS~4Cu~6Br~4(Py)~4]的合成及晶体结构

郎建平;郁开北;忻新泉   

  1. 苏州大学化学系;中国科学院成都分析测试中心;南京大学化学系
  • 发布日期:1996-03-15

Synthesis and crystal structure of a novel two- dimensional heptanuclear cluster compound [WS~4Cu~6Br~4(Py)~4]

LANG JIANPING;YU KAIBEI;XIN XINQUAN   

  • Published:1996-03-15

标题化合物是通过(NH~4)~2WS~4,CuBr和(n-Bu)~4NBr的低热固相反应,其固相产物的乙腈溶液和吡啶发生取代反应来合成的。此簇合物为四方晶系,空间群I4 2d,晶胞参数:α=1.4612(2)nm,c=1.5125(3)nm,V=3.2300(3)nm^3,Z=4,μ=126.90cm^-^1,D~c=2.73g/cm^3,F(000)=2479,最终偏差因子R=0.040。X射线单晶衍射法证实由六个Cu原子所组成的稍畸变的八面体,包围着近似正四面体的WS~4核,形成WS~4Cu~6单元,通过-Cu~e~q-Br-Cu~e~q-桥,此单元连接其最近的另一个单元,形成一个二维网络结构。

关键词: 晶体结构测定, X射线衍射分析, 吡啶, 铜络合物, 三苯基膦, 簇状化合物, 二维, 多核络合物, 硫络合物, 固相反应

The title compound [WS~4Cu~6Br~4(Py)~4] were obtained by the reaction of (NH~4)~2WS~4, CuBr and (n-Bu)~4NBr in the solidstate and pyridine substitution of the solid state product in acetonitrile. Its red crystal is tetragonal, space group I4 2d with unit cell parameters α=1.4612(2)nm, c=1.5125(3)nm, V=3.2300(3)nm^3, Z=4, μ=126.90cm^-^1, D~c=2.73g/cm^3, F(000)=2479, R=0.040 for 560 observed reflections. The X-ray analysis confirms that the structure, which possesses acrystallo- graphic 4 symmetry axis running through Br(1), Cu(1), W, Cu(1a), Br(1a) atoms, consists of a tetrahedral WS~4 core envelopedby an octahedral array of six copper atoms, forming an WS~4Cu~6 aggregate. Linked by -Cu~e~q-Br-Cu~e~q-bridges, this aggregate connects with its nearest, neighbours and develops a two-dimensional network.

Key words: CRYSTAL STRUCTURE DETERMINATION, X-RAY DIFFRACTION ANALYSIS, PYRIDINE, COPPER COMPLEX, TRIPHENYLPHOSPHINE, CLUSTER COMPOUND, TWO-DIMENSIONAL, POLYNUCLEAR COMPLEX, SULFIDE COMPLEX, SOLID PHASE REACTION

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