Synthesis, Crystal Structure, and Property of Novel Tetranuclear Nickel(II) Complex with Multidentate Ligand 7-((3,5-Dichloro-2-pyridyl)azo)-8-hydroxyquinoline-5-sulfonic Acid.
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概要
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Reaction of nickel(II) perchlorate with the title ligand (Hpahqs) in aqueous solution followed by standing for about six months produces a complex having the formulation [Ni<SUB>4</SUB>(pahqs)<SUB>4</SUB>(H<SUB>2</SUB>O)<SUB>4</SUB>]·20H<SUB>2</SUB>O. A single crystal X-ray analysis revealed that the complex contained the four nickel(II) and four ligand molecules and showed a novel structure of oxygen bridged tetranuclear nickel(II) complex. Crystal data: triclinic, space group <I>P</I>\bar1, <I>a</I>=17.884(7), <I>b</I>=22.071(8), <I>c</I>=12.819(8) Å, α=100.77(4)°, β=92.55(4)°, γ=71.46(4)°, <I>Z</I>=2. Except one N atom in each azo-group, all the other donor atoms in the ligand were fully used in coordination to nickel(II), forming either <I>N</I>,<I>N</I>,<I>O</I>- or <I>N</I>,<I>O</I>-chelate rings, simultaneously. The geometry around each of the four nickel(II) was distorted octahedron. The bond lengths of N<SUB>1</SUB>–N(N atoms in <I>N</I>,<I>N</I>,<I>O</I>-terdentate moieties) were elongated compared with those of the corresponding complex, and the lengths of N<SUB>1</SUB>–N(N atoms in quinoline rings) were kept almost similar values to those of the Ni(II)-8-hydroxyquinoline complex. The bond lengths of Ni–O were elongated compared with those of the nickel(II) complexes with either <I>N</I>,<I>N</I>,<I>O</I>- or <I>N</I>,<I>O</I>-chelate rings, resulting in the contraction of the angles of N–Ni–N or N–Ni–O. The angles of Ni–O–Ni around four nickel(II) sites were ca. 140°. The antiferromagnetic exchange interaction was operating between the four nickel(II) via bridging oxygen atoms.
- 公益社団法人 日本化学会の論文
著者
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Kai Fumiaki
Department Of Chemistry Faculty Of Science Kumanoto University
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Nakamura Masaaki
Department Of Applied Physics Faculty Of Science Tokyo University Of Science
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Huang Hu
Department of Chemistry, Faculty of Science, Kumamoto University
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Asai Yoshifumi
Department of Chemistry, Faculty of Science, Kumamoto University
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Hirohata Masaaki
Department of Chemistry, Faculty of Science, Kumamoto University
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