Structure and Polarized Spectra of cis-difluorotetraamminecobalt(III) Perchlorate, cis-(CoF2(NH3)4)ClO4.

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概要

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• The structure of <I>cis</I>-[CoF<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>]ClO<SUB>4</SUB> has been determined by a single-crystal X-ray diffraction method. Crystals are tetragonal, space group <I>P</I>4<SUB>1</SUB> (or <I>P</I>4<SUB>3</SUB>), <I>a</I>=7.2645(6), <I>c</I>=16.260(2) Å, <I>V</I>=858.1(2) Å<SUP>3</SUP>, <I>Z</I>=4,<I>T</I>=297(1) K, final <I>R</I>=0.052 for 970 observed unique reflections. The coordinated F and N atoms could be distinguished unambiguously from each other based on the thermal parameters. The bond distances Co–F and Co–N are 1.828(6)–1.870(5) and 1.924(7)–1.944(7) Å, respectively. The absorption spectra of the single crystals have been examined in the visible and infrared regions with polarized radiation by the use of microspectrophotometers. The 584 nm band (<I>B</I><SUB>1</SUB>) was considered to borrow intensity from some <I>A</I><SUB>1</SUB> bands through vibronic coupling with some <I>B</I><SUB>1</SUB> vibrations, and the 504 nm band (<I>A</I><SUB>2</SUB> & <I>B</I><SUB>2</SUB>) through some <I>A</I><SUB>2</SUB> and <I>B</I><SUB>2</SUB> vibrations. Two of the four ammine groups of this cobalt complex were found to give an NH<SUB>3</SUB> rocking frequency (860 cm<SUP>−1</SUP>) higher by 50 cm<SUP>−1</SUP> than the other two (at 810 cm<SUP>−1</SUP>). This fact has been attributed to two inter-molecular hydrogen bonds (NH···F=2.85–2.68 Å) in which the former two ammine groups are involved.

• 公益社団法人 日本化学会の論文

著者

• Tsuboi Masamichi

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• Saito Yoshihiko

  Department Of Cardiology Juntendo University School Of Medicine

• Mitsutsuka Yoshihiro

  Department Of Chemistry College Of Science And Technology Meisei University

• OHBA SHIGERU

  Deparment of Biology, Faculty of Science, Tokyo Metropolitan University

• Aoyama Tomonori

  Department of Chemistry, Faculty of Science & Technology, Keio University

• Kaneuchi Fumiko

  Japan Spectroscopy Co., Ltd.

• Saito Yoshihiko

  Department of Chemistry, Faculty of Science & Technology, Keio University

• Mitsutsuka Yoshihiro

  Department of Chemistry, Faculty of Science & Engineering, Meisei University

• Tsuboi Masamichi

  Faculty of Science & Engineering, Iwaki-Meisei University

• Tsuboi Masamichi

  Faculty of Parmaceutical Sciences, The University of Tokyo

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