Electronic spectrum and magnetic properties of a dinuclear nickel(II) complex with two nickel(II) ions of C2-twisted octahedral geometry |
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Authors: | Hiroshi Sakiyama Katsuya Tone Masahiro Mikuriya |
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Institution: | a Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, Kojirakawa, Yamagata 990-8560, Japan b X-Ray Research Laboratory, Rigaku Corporation, Matsubara 3-9-12, Akishima, Tokyo 196-8666, Japan c Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, Gakuen 2-1, Sanda 669-1337, Japan |
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Abstract: | A dinickel(II) complex Ni2(sym-hmp)2](BPh4)2·3.5DMF·0.5(2-PrOH) (1) was synthesized with a dinucleating ligand, 2,6-bis(2-hydroxyethyl)methylaminomethyl]-4-methyl-phenol H(sym-hmp)]. The complex 1 (C90H118.50B2N7.50Ni2O10) crystallized in the triclinic space group with dimensions a = 14.7446(4) Å, b = 15.4244(4) Å, c = 18.7385(6) Å, α = 86.9495(9)°, β = 76.7263(10)°, γ = 86.5370(8)°, and V = 4136.8(2) Å3 and with Z = 2; this is isomorphous to a previous cobalt(II) complex Co2(sym-hmp)2](BPh4)2. Single-crystal X-ray analysis revealed a bis(μ-phenoxo)dinickel(II) core structure containing two distorted octahedral nickel(II) ions of C2 symmetry. The order of the coordination bond lengths is Ni-O(phenoxo) < Ni-O(hydroxy) < Ni-N. The electronic spectrum of 1 was typical for the octahedral nickel(II) complexes, but the axial elongation and the C2-twist of the equatorial plane were found after a detailed analysis. The bond angles obtained by the electronic spectrum agreed with the crystallographically obtained bond angles within 2.3°. The order of the AOM parameters was eσ,O(phenoxo) > eσ,O(hydroxy) > eσ,N, which was consistent with the order of the coordination bond lengths. Magnetic susceptibility data for 1 were fitted well with the parameters 2J = −69.7 cm−1, D = 0.00 cm−1, g = 2.17, and TIP = 265 × 10−6 cm3 mol−1. The result indicates significant antiferromagnetic exchange interaction and negligible zero-field splitting, while the isostructural cobalt(II) complex showed an anisotropic behavior. |
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Keywords: | Dinuclear nickel(II) complex Crystal structure Electronic spectrum Magnetic properties |
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