类晶加合物(M=Co,Cu,Ni)的晶体结构及分子间相互作用的理论研究  

Theorelical Study of Crystal Structures and Intermolecular Interactions in Isomorphous Adducts [2-ClPyH]_2^+ [MCl_4^(2-)](M=Co,Cu,Ni)

作　　者：白娟[1] 王果[1] 张莉[1] 王超[1] 黄元河[1] 方德彩[1] 李奇[1] 

机构地区：[1]北京师范大学化学学院,北京100875

出　　处：《高等学校化学学报》2007年第6期1113-1116,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20571012);北京市自然科学基金(批准号:2042013)资助

摘　　要：合成了3种化合物[2-ClPyH]2CoCl4(1),[2-ClPyH]2NiCl4(2)和[2-ClPyH]2CuCl4(3),单晶X射线衍射法晶体结构测定结果表明,这3种化合物是同形加合物,在它们的结构中,[2-ClPyH]+离子呈平面状,而[MCl4]2-离子为变形的四面体.晶体结构分析发现晶体中存在N—H…Cl和C—H…Cl氢键,以及Cl…Cl分子间相互作用和π-π堆积作用.对自由状态下独立的配位离子进行的几何构型优化,以及三维周期性条件下几何结构优化的量子化学计算结果表明,标题化合物中具有方向性和选择性的氢键决定延伸性结构的方向,而相对较弱的卤素…卤素作用在最终晶体结构的确定中扮演很重要的角色.Three complexes [2-ClPyH]2CoCl4（ l ）,[2-ClPyH]2NiCl4（2） and [2-ClPyH]2CuCl4（3） were prepared, and their crystal structures were determined with X-ray crystallography. In each of the structures, the [2-ClPyH ]^＋ cation is almost in the same plane while the [MCl4]^2- anion is a slightly distorted tetrahed-ton. The X-ray crystallography analysis indicates that ultimate structures include the hydrogen bonds N-H…CI and C-H…Cl, intermolecular Cl…Cl interactions as well as π-π stacking interactions. The title com-pounds were investigated theoretically via crystal orbital method based on density functional theory, as self-ex-istent anions and a structure units respectively. The hydrogen bonding determines the directions of one-dimen- sional infinite columns and Cl...Cl interactions plays a crucial role in the final structure.

关 键 词：加合物 氢键 C1…cl作用 Π-Π堆积作用 

分 类 号：O641.1[理学—物理化学]