Synthesis,Crystal Structure and Quantum Chemistry Study on[CoⅢ(DIEN)(N3)3]Complex
Adopting ligand occupation strategy and the principle of molecular self-assembly,a mononuclear cobalt(Ⅲ)complex[CoⅢ(DIEN)(N3)3](1,DIEN=diethylenetriamine)was synthesized by solution method using diethylenetriamine as the organic ligand and Co3+as the central metal ion at room temperature.Single crystal of complex 1 was obtained.The structural characterization and electronic structure analysis were carried out through X-ray single crystal diffraction,elemental analysis,and quantum chemical calculations.Single crystal X-ray diffraction analysis reveals that complex 1 is triclinic,space group of P(1)with a=0.825 3(2)nm,b=0.892 0(3)nm,c=0.898 7(3)nm,α=106.497(4)°,β=90.281(4)°,γ=113.861(4)°,V=0.574 7(3)nm3.The central ion Co(Ⅲ)has an elongated octahedral configuration.Each complex is composed of Co3+cation,three azide anions and one diethylenetriamine ligand.A disordered azide anion has a site occupancy of 50％,and 1D chain-like supermolecular was formed by N—H … N hydrogen bond and π … π packing interations.In addition,based on crystal structure of complex 1 determined by X-ray crystallographic analysis,the full geometry optimized and frequency calculations have been performed by density functional theory.The single-point energy,atomic charges and frontier molecular orbital were analyzed.The theoretical calculation results indicate that the complex configuration is stable and consistent with the experimental results.
Co(Ⅲ)supramolecular complexcrystal structurequantum chemical calculationdensity functional theoryatomic chargefrontier molecular orbital
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