高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

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

白娟, 王果, 张莉, 王超, 黄元河, 方德彩, 李奇   

  1. 北京师范大学化学学院, 北京 100875
  • 收稿日期:2006-05-30 修回日期:1900-01-01 出版日期:2007-06-10 发布日期:2007-06-10
  • 通讯作者: 李奇

Theorelical Study of Crystal Structures and Intermolecular Interactions in Isomorphous Adducts [2-ClPyH]2+[MCl42-](M=Co, Cu, Ni)

BAI Juan, WANG Guo, ZHANG Li, WANG Chao, HUANG Yuan-He, FANG De-Cai, LI Qi*   

  1. College of Chemistry, Beijing Normal University, Beijing 100875, China
  • Received:2006-05-30 Revised:1900-01-01 Online:2007-06-10 Published:2007-06-10
  • Contact: LI Qi

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被引次数

1

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.

关键词: 加合物, 氢键, Cl…Cl作用, π-π堆积作用

Abstract: Three complexes [2-ClPyH]2CoCl4(1), [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 tetrahedron. The X-ray crystallography analysis indicates that ultimate structures include the hydrogen bonds N—H…Cl and C—H…Cl, intermolecular Cl…Cl interactions as well as π-π stacking interactions. The title compounds were investigated theoretically via crystal orbital method based on density functional theory, as self-existent anions and a structure units respectively. The hydrogen bonding determines the directions of one-dimensional infinite columns and Cl…Cl interactions plays a crucial role in the final structure.

Key words: Adduct, Hydrogen bonds, Cl…Cl interaction, π-π Stacking interaction

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