Moon Dohyun, Choi Jong-Ha
Pohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea.
Department of Chemistry, Andong National University, Andong 36729, Republic of Korea.
Acta Crystallogr E Crystallogr Commun. 2016 Mar 4;72(Pt 4):456-9. doi: 10.1107/S205698901600356X. eCollection 2016 Apr 1.
The asymmetric unit of the title complex salt, [Cr(C10H24N4)(NH3)2][ZnCl4]Cl·H2O, is comprised of four halves of the Cr(III) complex cations (the counterparts being generated by application of inversion symmetry), two tetra-chlorido-zincate anions, two chloride anions and two water mol-ecules. Each Cr(III) ion is coordinated by the four N atoms of the cyclam (1,4,8,11-tetra-aza-cyclo-tetra-deca-ne) ligand in the equatorial plane and by two N atoms of ammine ligands in axial positions, displaying an overall distorted octa-hedral coordination environment. The Cr-N(cyclam) bond lengths range from 2.0501 (15) to 2.0615 (15) Å, while the Cr-(NH3) bond lengths range from 2.0976 (13) to 2.1062 (13) Å. The macrocyclic cyclam moieties adopt the trans-III conformation with six- and five-membered chelate rings in chair and gauche conformations. The ZnCl4 anions have a slightly distorted tetra-hedral shape. In the crystal, the Cl(-) anions link the complex cations, as well as the solvent water mol-ecules, through N-H⋯Cl and O-H⋯Cl hydrogen-bonding inter-actions. The supra-molecular set-up also includes N-H⋯Cl, C-H⋯Cl, N-H⋯O and O-H⋯Cl hydrogen bonding between N-H or C-H groups of cyclam, ammine N-H and water O-H donor groups, and O atoms of the water mol-ecules, Cl(-) anions or Cl atoms of the ZnCl4 anions as acceptors, leading to a three-dimensional network structure.
标题配合物盐[Cr(C₁₀H₂₄N₄)(NH₃)₂][ZnCl₄]Cl·H₂O的不对称单元由四个Cr(III)配合物阳离子的一半(通过反演对称性产生对应部分)、两个四氯合锌酸根阴离子、两个氯离子和两个水分子组成。每个Cr(III)离子在赤道平面上由环戊二烯(1,4,8,11-四氮杂环十四烷)配体的四个N原子配位,在轴向位置由两个氨配体的N原子配位,呈现出整体扭曲的八面体配位环境。Cr-N(环戊二烯)键长范围为2.0501 (15)至2.0615 (15) Å,而Cr-(NH₃)键长范围为2.0976 (13)至2.1062 (13) Å。大环环戊二烯部分采用反式-III构象,六元螯合环呈椅式构象,五元螯合环呈扭曲构象。ZnCl₄阴离子具有轻微扭曲的四面体形状。在晶体中,Cl(-)阴离子通过N-H⋯Cl和O-H⋯Cl氢键相互作用连接配合物阳离子以及溶剂水分子。超分子结构还包括环戊二烯的N-H或C-H基团、氨N-H和水O-H供体基团与水分子的O原子、Cl(-)阴离子或ZnCl₄阴离子的Cl原子之间的N-H⋯Cl、C-H⋯Cl、N-H⋯O和O-H⋯Cl氢键,形成三维网络结构。