Part 8
Crystal Structure of a Mixed-valent Hexanuclear Manganese Complex Made-up from Two Oxido-centered Triangular MnIIMnIII2 Cores
2021 年 37 巻 p. 41-43
詳細
2021 年 37 巻 p. 41-43
A hexanuclear MnII2MnIII4 complex with 2-(5-nitro-2-hydroxyphenyl)-1,3-bis(2-(5-nitro-2-hydroxybenzylideneamino)ethyl)imidazolidine (H3LNO2) and its hydrolyzed ligand, 1,10-bis(5-nitrosalicylideneamino)-4,7-azadecane (H2LNO2′), 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-LNO2)}2(LNO2′)]·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)Å3, Dcalcd = 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 LNO2′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 LNO23−, 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 MnII2MnIII4 state with the MnII state for the Mn1 atom and the MnIII state for the Mn2 and Mn3 atoms, respectively.
