(H_2en)_2[Se_2Mo_5O_(21)]2H_2O的水热合成、晶体结构与光谱研究  

Hydrothermal Synthesis, Crystal Structure and Spectroscopic Analysis of (H_2en)_2[Se_2Mo_5O_(21)]2H_2O

作　　者：连照勋[1] 黄长沧[1] 张汉辉[1] 黄细河[1] 杨宏芳[1] 

机构地区：[1]化学系和固体材料化学重点实验室

出　　处：《Chinese Journal of Structural Chemistry》2004年第6期605-611,共7页结构化学（英文）

基　　金：福建省自然科学基金(E00110013);省科技三项基金(K02028);省教育厅资金( JA00137);福州大学科技发展基金(XKJ-QD-00-06)

摘　　要：在水热条件下, 以SeO2、V2O5、MoO3、K2CO3、en(乙二胺)作为起始原料, 得到了标题化合物(H2en)2[Se2Mo5O21]2H2O, 利用IR、UV、荧光光谱、单晶-X射线衍射等方法对其进行了表征。结构测定表明, 该化合物属于正交晶系, 空间群: P212121, 化学式: C4H24- Mo5N4O23Se2, 晶胞参数: a = 12.1386(7), b = 17.7118(8), c =11.7092(5) ? V = 2517.4(2) ?, Z = 4, Dc = 2.987 g/cm3, Mr = 1133.89, m = 5.419 mm-1, F(000) = 2144, 最终结构偏离因子R = 0.0285, wR = 0.0400, S = 0.904。该化合物由2个双质子化的en、2个H2O分子以及杂多阴离子[Se2Mo5O21]4-组成。其中,杂多阴离子由5个畸变的MoO6八面体以共边或共顶点形式连接构成一个平面骨架; 2个畸变的SeO3四面体和MoO6八面体以共顶点形式连接, 且位于平面的两侧;质子化的en位于4个[Se2Mo5O21]4-离子围成的四面体空位中, 与杂多阴离子和水分子通过氢键连接成无限三维结构。最后我们用B3LYP方法研究了阴离子簇的电子结构。The title compound was synthesized under hydrothermal condition with SeO2, V2O5, MoO3, K2CO3 and en, and characterized by X-ray crystal-structure analysis, IR, UV-Vis DRIS and fluorescence spectra. It belongs to orthorhombic, space group P212121 with a = 12.1386(7), b = 17.7118(8), c = 11.7092(5) , V = 2517.4(2) ?, Z = 4, Dc = 2.987 g/cm3, Mr = 1133.89, m = 5.419 mm-1, F(000) = 2144, R = 0.0285, wR = 0.0400 and S = 0.904. The title compound contains two biprotonized en cations, five distorted MoO6 octahedra and two SeO3 pyramids by sharing vertices and edges. These five Mo atoms are nearly coplanar, and two SeO3 pyramids lie on both sides of this plane. H2en lies in the tetrahedron made up of four [Se2Mo5O21]4-. The H2en molecules are connected with the anion and water by hydrogen bonds to form a three-dimensional structure. At last, we also discussed the electron structure of the cluster anion with the B3LYP method.

关 键 词：乙二胺 硒 Strandberg型 杂多化合物 水热合成 晶体结构 钼 

分 类 号：O614[理学—无机化学]