Stereochemical properties of copper(II) complexes of (S)-3-aminohexahydroazepine. Crystal and molecular structure of bromobis[(S)-3-aminohexahydroazepine]copper(II) perchlorate[CuBr(S-ahaz)2]ClO4.

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概要

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• A series of copper(II) complexes of (<I>S</I>)-3-aminohexahydroazepine (abbreviated as <I>S</I>-ahaz) were prepared. The molecular structure of bromobis[(<I>S</I>)-3-aminohexahydroazepine]copper(II) perchlorate, [CuBr(<I>S</I>-ahaz)<SUB>2</SUB>]ClO<SUB>4</SUB>, was determined using single-crystal X-ray diffraction method. The complex crystallizes is space group <I>P</I>2<SUB>1</SUB>2<SUB>1</SUB>2<SUB>1</SUB> with <I>a</I>=13.449(6), <I>b</I>=17.411(11), <I>c</I>=7.937(2) Å, and <I>Z</I>=4. The structure was solved by the direct method and refined by the least squares to <I>R</I> value of 0.068 for 1853 unique reflections. The Cu<SUP>2+</SUP> ion has the square-pyramidal five-coordination geometry with four nitrogen atoms as basal donors and a bromide as an apical donor. The structures of other copper(II) complexes of <I>S</I>-ahaz were assigned on the basis of the above X-ray analysis result, together with electronic spectral and conductivity measurements. The complexes having the formula Cu(<I>S</I>-ahaz)<SUB>2</SUB>X(ClO<SUB>4</SUB>) (X<SUP>−</SUP>=CI<SUP>−</SUP>, I<SUP>−</SUP>, NCS<SUP>−</SUP>, ONO<SUP>−</SUP>) were assigned to have square-pyramidal five-coordinated structures. The <I>S</I>-ahaz complexes Cu(<I>S</I>-ahaz)<SUB>2</SUB>X<SUB>2</SUB> (X<SUP>−</SUP>=Cl<SUP>−</SUP>, Br<SUP>−</SUP>, NO<SUB>3</SUB><SUP>−</SUP>) were also considered to have similar five-coordination geometries, while the complexes Cu(<I>S</I>-ahaz)<SUB>2</SUB>X<SUB>2</SUB> (X<SUP>−</SUP>=ClO<SUB>4</SUB><SUP>−</SUP>, BF<SUB>4</SUB><SUP>−</SUP>) to be four-coordinated in the crystalline state.

• 公益社団法人 日本化学会の論文

著者

• Miyamura Kazuo

  Department Of Anesthesiology National Mie Chuo Hospital

• Yoshikawa Sadao

  Department Of Applied Chemistry Faculty Of Science And Technology Keio University

• Saburi Masahiko

  Department Of Applied Chemistry Saitama Institute Of Technology

• Sakurai Tosio

  Institute Of Science And Technology University Of Tokyo

• Mizoguchi Yasuo

  Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo

• Tsuboyama Sei

  Institute of Physical and Chemical Research

• Morita Masatoshi

  Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo

• Tsuboyama Kaoru

  Institute of Physical and Chemical Research

• Sakurai Tosio

  Institute of Physical and Chemical Research

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