X-ray structures of Cu(II) chelates of cis-1,3-cyclohexanediamine.

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概要

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• The crystal structures of wine-red [Cu(1,3-chxn)<SUB>2</SUB>]Br<SUB>2</SUB> (<B>1</B>), [Cu(1,3-chxn)<SUB>2</SUB>](NO<SUB>3</SUB>)<SUB>2</SUB> (<B>2</B>), and blue-violet [CuCl(1,3-chxn)<SUB>2</SUB>]ClO<SUB>4</SUB> (<B>3</B>) (1,3-chxn=<I>cis</I>-1,3-cyclohexanediamine) have been determined from the diffractometer data measured by the use of Mo <I>K</I>α radiation. The structures were solved by the Patterson–Fourier method and refined by the least-squares method to <I>R</I>=0.042 (<B>1</B>), 0.033 (<B>2</B>), and 0.057 (<B>3</B>) for 1309, 1210, and 776 nonzero reflections respectively. The Cu atoms in <B>1</B> and <B>2</B> have a square-planar coordination by 4 N atoms, while the complex ion in <B>3</B> has a 5-coordinate square-pyramidal geometry, with the Cl atom at the apical position. The 6-membered chelate rings in <B>1</B>, <B>2</B>, and <B>3</B> are of the chair, flattened-chair, and envelope conformations respectively. The complex ions in <B>1</B> and <B>2</B> have virtually a C<SUB>2h</SUB> symmetry, the two-fold axis of which lies on the CuN<SUB>4</SUB> plane. The virtual symmetry for [CuCl(1,3-chxn)<SUB>2</SUB>]<SUP>+</SUP> is C<SUB>2v</SUB>, the approximate two-fold axis being coincident with the Cu–Cl bond. The cyclohexane rings (chair conformation) in <B>2</B> and <B>3</B> are roughly perpendicular to the coordination plane, but that in <B>1</B> leans toward the central Cu(II) atom. The formation of such coordinatively unsaturated Cu(II) complexes as <B>1</B>–<B>3</B> is attributable to the steric hindrance of the bulky cyclohexane ring to the axial coordination site.

• 公益社団法人 日本化学会の論文

著者

• Matsumoto Keiji

  Department Of Applied Physics Graduate School Of Engineering Yokohama National University

• Kidani Yoshinori

  Faculty Of Pharmaceutical Sciences Nagoya City University

• Saito Reiko

  Aichi Junior College of Nursing

• Kamisawa Keiko

  Department of Chemistry, Faculty of Science, Osaka City University

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