Crystal Structure of a Mixed-valent Hexanuclear Manganese Complex Made-up from Two Oxido-centered Triangular Mn^IIMn^III₂ Cores

• MIKURIYA Masahiro

  Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University

• ONO Sayuri

  Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University

• KOYAMA Yoshiki

  Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University

• MITSUHASHI Ryoji

  Institute of Liberal Arts and Science, Kanazawa University

• TSUBOI Motohiro

  Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University

Abstract

A hexanuclear Mn^II₂Mn^III₄ complex with 2-(5-nitro-2-hydroxyphenyl)-1,3-bis(2-(5-nitro-2-hydroxybenzylideneamino)ethyl)imidazolidine (H₃L_NO2) and its hydrolyzed ligand, 1,10-bis(5-nitrosalicylideneamino)-4,7-azadecane (H₂L_NO2′), was isolated. The crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The complex crystallized as [{Mn₃(μ₃-O)(μ-CH₃COO)₂(μ-L_NO2)}₂(L_NO2′)]·2.5THF·CH₃OH in the monoclinic space group C2/c with a = 21.253(3), b = 16.630(2), c = 29.508(4)Å, β = 93.147(2)°, V = 10413(2)ų, D_calcd = 1.551 g/cm³, Z = 4. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0836 and 0.2500, respectively, for all 11924 independent reflections. The complex is a hexanuclear manganese molecule which has a crystallographic inversion center at the midpoint of the ethylenediamine backbone of L_NO2′²⁻ ligand. In the asymmetric unit, three manganese atoms (Mn1, Mn2, and Mn3) are arranged in a μ₃-oxido-centered triangle, and the Mn1 and Mn2 atoms are further bridged by a phenolato-oxygen atom of L_NO2³⁻, and both of the Mn1 and Mn3 atoms and the Mn2 and Mn3 atoms are further bridged by an acetato ligand in a syn-syn mode. The charge balance and a bond valence sum calculation supported the mixed-valent Mn^II₂Mn^III₄ state with the Mn^II state for the Mn1 atom and the Mn^III state for the Mn2 and Mn3 atoms, respectively.

Journal

• X-ray Structure Analysis Online

  X-ray Structure Analysis Online 37 (0), 41-43, 2021-08-10

  The Japan Society for Analytical Chemistry

Keywords

• Materials Chemistry
• Analytical Chemistry

Details

• CRID: 1390570465068790528
• NII Article ID: 130008072689
• DOI: 10.2116/xraystruct.37.41
• ISSN: 18833578
• Web Site: https://www.jstage.jst.go.jp/article/xraystruct/37/0/37_41/_pdf
• Text Lang: en
• Data Source:
  • JaLC
  • Crossref
  • CiNii Articles
  • KAKEN
• Abstract License Flag: Disallowed