X-Ray Crystal Structures of Octahedral Diaquabis(N,N-dialkyl-ethylenediamine)nickel(II) Complexes Possessing Elongated Nickel(II)-Nitrogen Bonds along Axial Direction.
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概要
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The structures of two diaquabis(<I>N</I>,<I>N</I>-dialkylethylenediamine)nickel(II) chlorides ([Ni(H<SUB>2</SUB>O)<SUB>2</SUB>(diamine)<SUB>2</SUB>]Cl<SUB>2</SUB>·<I>n</I>H<SUB>2</SUB>O) were determined by X-ray crystallographic studies, where diamine is <I>N</I>,<I>N</I>-dimethylethylenediamine(<I>NN</I>-dmen) or <I>N</I>,<I>N</I>-diethylethylenediamine (<I>NN</I>-deen). Both complexes are trans and crystallize in the monoclinic space group <I>P</I>2<SUB>1</SUB>⁄<I>n</I>. The unit cell parameters of the <I>NN</I>-dmen complex, NiCl<SUB>2</SUB>C<SUB>8</SUB>N<SUB>4</SUB>O<SUB>2</SUB>H<SUB>32</SUB>, are <I>a</I>=7.531(1), <I>b</I>=13.092(1), <I>c</I>=9.591 Å, β=107.76(1)°, and <I>Z</I>=2, and those of the <I>NN</I>-deen complex, NiCl<SUB>2</SUB>C<SUB>12</SUB>N<SUB>4</SUB>O<SUB>2</SUB>H<SUB>36</SUB>, are <I>a</I>=9.154(1), <I>b</I>=8.692(1), <I>c</I>=12.395(2) Å, β=104.46(1)°, and <I>Z</I>=2. In <I>trans</I>-[Ni(H<SUB>2</SUB>O)<SUB>2</SUB>(<I>NN</I>-dmen)<SUB>2</SUB>]Cl<SUB>2</SUB>·2H<SUB>2</SUB>O and <I>trans</I>-[Ni(H<SUB>2</SUB>O)<SUB>2</SUB>(<I>NN</I>-deen)<SUB>2</SUB>]Cl<SUB>2</SUB>, the Ni–NMe<SUB>2</SUB> and Ni–NEt<SUB>2</SUB> bond distances (2.183 and 2.271 Å) are much longer than the Ni–NH<SUB>2</SUB> distances (2.078 and 2.064 Å), forming tetragonally distorted octahedrons with four close in-plane neighbors(N<SUB>2</SUB>O<SUB>2</SUB>) and two remote axial ones(N<SUB>2</SUB>). It is apparent that this distortion originates from the steric requirement of N-substituted groups. Such a distortion significantly affects the electronic spectra of these complexes.
- 公益社団法人 日本化学会の論文
著者
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Fujimoto Yumi
Laboratory Of Animal Reproduction Faculty Of Agriculture Kagoshima University
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Uehara Akira
Department Of Chemistry Faculty Of Science Kanazawa University
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SUZUKI Masatatsu
Department of Chemistry, Faculty of Science, Kanazawa University
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Ihara Yoshinori
Laboratory Of Chemistry Faculty Of Education Kanazawa University
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Satake Yasuhiro
Department of Chemistry, Faculty of Science, Kanazawa University
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Senda Hitoshi
Laboratory of Chemistry, Faculty of Liberal Arts, Kanazawa University
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