一例含阴离子水簇的钴配合物的合成、结构及理论研究

摘要/Abstract

摘要： 金属配合物中的水簇研究为研究宏观意义上的水以及与蛋白质分子有关的水分子提供了有效途径。本文合成了一个含有阴离子水簇的带状超分子配合物[Co(2,2-bipy)₂(N₃)₂](N₃)_0.5Cl_0.5·2H₂O(1,2, 2-bipy=2, 2-联吡啶)。单晶结构解析表明,配合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.822 54(7) nm,b=1.175 58(9) nm,c=1.237 06(10) nm,α=91.379 0(10)°,β=92.151 0(10)°,γ=108.119 0(10)°,V=1.135 27(16) nm³,由一个单核[Co(2,2-bipy)₂(N₃)₂]⁺配合物阳离子、两个非配位水分子、0.5个游离的叠氮离子和0.5个氯离子组成,叠氮离子和氯离子位置无序,占有率各为50%。两个客体水分子通过强烈的分子间氢键作用形成了环状水四聚体,且与无序的N^-₃和Cl^-通过氢键作用形成了一个[(H₂O)₄(N₃)Cl]²^- 阴离子水簇。此外,本文基于密度泛函理论(DFT)对配合物[Co(2,2-bipy)₂(N₃)₂]⁺阳离子进行了量子化学计算,分析了其单点能和原子电荷,并计算了中心金属离子的氧化态,计算结果与实验相吻合。

关键词: 阴离子水簇, 金属配合物, 钴, 密度泛函理论, 晶体结构, 水四聚体

Abstract: Water clusters in metal complexes provide an effective way for the study on water in a macroscopic sense and water molecules related to protein molecules. In this paper, a supramolecular complex: [Co(2,2-bipy)₂(N₃)₂](N₃)_0.5Cl_0.5·2H₂O (1, 2,2-bipy=2,2-bipyridine) containing an anion-water cluster was synthesized using 2,2-bipyridine and azide ion as ligands. Single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in triclinic, P-1 space group with a=0.822 54(7) nm, b=1.175 58(9) nm, c=1.237 06(10) nm, α=91.379 0(10)°, β=92.151 0(10)°, γ=108.119 0(10)°, V=1.135 27(16) nm³, and it is composed of a mononuclear [Co(2,2-bipy)₂(N₃)₂]⁺ cation, two non-coordinating water molecules, 0.5 free azide and chloride anions. The disordered azide and chloride anions have a site occupancy of 0.5, respectively. The [Co(2,2-bipy)₂(N₃)₂]⁺ cations are connected to form a ribbon one-dimensional supramolecular structure through intermolecular C—H…π and π…π interactions. Two free water molecules and their crystallographically equivalent H₂O molecules are connected each other to form a cyclic water tetramer by strong intermolecular hydrogen bonds, and then, a [(H₂O)₄(N₃)Cl]^2- anion-water cluster is obtained by the strong intermolecular hydrogen bonds between free water molecules and disordered N^-₃ or Cl^- ions. The quantum calculation of complex [Co(2,2-bipy)₂(N₃)₂]⁺ has been performed by density functional theory method. The single point energy and atomic charge were analyzed, and the oxidation state of the central metal ion was calculated. The results of the calculation are consistent with the experiments.

Key words: anion-water cluster, metal complex, Co, density functional theory, crystal structure, water tetramer

中图分类号:

O614

李慧玲, 杨敏, 孙金, 李荣春, 魏荣敏. 一例含阴离子水簇的钴配合物的合成、结构及理论研究[J]. 人工晶体学报, 2021, 50(12): 2293-2299.

LI Huiling, YANG Min, SUN Jin, LI Rongchun, WEI Rongmin. Synthesis, Crystal Structure and Theory Studies of a Cobalt Complex with Anion-Water Cluster[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(12): 2293-2299.

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