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

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.

Theorelical Study of Crystal Structures and Intermolecular Interactions in Isomorphous Adducts [2-ClPyH]+2 [MCl2-4](M=Co, Cu, Ni)

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.