Structural, Magnetic, and Spectroscopic Characterization of the Pyridine Complexes of Copper(II) Triphenylacetate: A Dimeric Copper(II) Triphenylacetate-Pyridine Complex with Distorted Trigonal Bipyramidal Geometry Around Copper.

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概要

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• The synthesis and characterization of three copper(II) triphenylacetate-pyridine complexes are reported along with their magnetic and spectral properties: [Cu<SUB>2</SUB>(O<SUB>2</SUB>CCPh<SUB>3</SUB>)<SUB>4</SUB>(py)<SUB>2</SUB>]·C<SUB>6</SUB>H<SUB>6</SUB> (<B>1</B>), [Cu<SUB>2</SUB>(O<SUB>2</SUB>CCPh<SUB>3</SUB>)<SUB>4</SUB>(py)<SUB>2</SUB>] (<B>2</B>), and Cu(O<SUB>2</SUB>CCPh<SUB>3</SUB>)<SUB>2</SUB>·2py (<B>3</B>). Crystal structure analyses of <B>1</B> and <B>3</B> have revealed unusual geometries around copper: <B>1</B>, triclinic, space group <I>P</I>\bar1 with <I>a</I>=19.558(7) <I>b</I>=16.605(6), <I>c</I>=14.997(5) Å, α=14.55(2)°, β=97.11(2)°, γ=111.65(2)°, and <I>Z</I>=2; <B>3</B>, monoclinic, space group <I>P</I>2<SUB>1</SUB>⁄<I>c</I> with <I>a</I>=8.931(1), <I>b</I>=12.602(1), <I>c</I>=19.578(1) Å, β=118.17(0.4)°, and <I>Z</I>=2. The coordination sphere around each copper in the dimeric complex <B>1</B> is a highly distorted trigonal bipyramid with bridging triphenylacetato ligands spanning the apical and equatorial positions, resulting in a long Cu–Cu distance of 3.086(1) Å. Temperature-dependent magntic susceptibility measurements on <B>1</B> indicate that the two coppers are antiferromagnetically coupled with −2<I>J</I>=187 cm<SUP>−1</SUP>. The structure of the monomeric complex <B>3</B> is unusual in that the out-of-plane carboxylate oxygen is twisted 12° from the normal. Two solid modifications are observed for <B>2</B>. The magnetic and spectral properties of <B>2a</B> (−2<I>J</I>=173 cm<SUP>−1</SUP>) resemble those of <B>1</B>, and <B>2b</B> (−2<I>J</I>=321 cm<SUP>−1</SUP>) those of copper(II) acetate monohydrate. Magneto-structural correlations are presented. The novel structural features of these complexes are suggested to arise from steric effects resulting from the spatial relationships both between and within the molecules in the crystal environment.

著者

• Tokii Tadashi

  Department Of Chemistry And Applied Chemistry Facukty Of Science And Engineering Saga University

• Steward Omar

  Department Of Chemistry And Biochemistry Duquesne University

• Chang Shih-chi

  Department Of Electronic Engineering St. John's University

• Muto Yoneichiro

  Department Of Chemistry Faculty Of Science And Engineering Saga University

• Taura Toshiaki

  Department of Chemistry, Faculty of Science, Hiroshima University

• Kato Michinobu

  Department of Chemistry, Aichi Prefectural University

• Sax Martin

  Biocrystallography Laboratory, V A Medical Center

• Chang Chong-Hwan

  Biocrystallography Laboratory, V A Medical Center

• Jury C.

  Department of Chemistry and Physics, Duquesne University

• Pletcher James

  Biocrystallography Laboratory, V A Medical Center

• Yoo Chung

  Biocrystallography Laboratory, V A Medical Center

• Chang Shih-Chi

  Department of Chemistry and Physics, Duquesne University

• Steward Omar

  Department of Chemistry and Physics, Duquesne University

• Taura Toshiaki

  Department of Chemistry, Aichi Prefectural University

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