Synthesis, Crystal Structure and Theory Studies of a Cobalt Complex with Anion-Water Cluster

Abstract

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

CLC Number:

O614

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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