Trinuclear and Dinuclear Manganese Complexes of 2/4-Formylbenzoic Acid Oxime Ligands:Syntheses and C

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Two manganese complexes, [Mn3(2-cba)6(phen)2] 1 (2-cba = 2-cyanobenzoic acid, phen = 1,10-phenanthroline) and [Mn2(4-fbao)2(phen)4](PF6)2·2H2O 2 (4-fbao = 4-formylbenzoic acid oxime), have been synthesized by the reaction of 2-formylbenzoic acid oxime (2-fbao, H2L1) or 4-formylbenzoic acid oxime (4-fbao, H2L2) with phen and manganese acetate in ethanol or methanol solution. A translation from the oximino (-CHN=OH) of H2L1 to cyano (-C≡N) was found in the formation of complex 1 at room temperature. The complexes were structurally determined by single-crystal X-ray diffraction. The crystal of compound 1 belongs to monoclinic, space group C2/c, with a = 17.983(6), b = 23.364(7), c =14.589(5) , β = 92.401(5)o, V = 6124(3) 3, Z = 4, C72H40Mn3N10O12, Mr = 1401.96, Dc = 1.521 g/cm3, F(000) = 2852.0, Rint = 0.0372, T = 293(2) K, μ = 0.686 mm-1, the final R = 0.0644 and wR = 0.1813 for 5803 observed reflections with I > 2σ(I). The crystal of compound 2 is of monoclinic system, space group P21/n, with a = 13.050(4), b = 20.577(5), c = 13.323(4) , β = 113.578(3)o, V = 3227.2(14) 3, Z = 2, C64H48F12Mn2N10O8P2, Mr = 1484.94, Dc = 1.528 g/cm3, F(000) = 1508.0, Rint = 0.0295, T = 293(2) K, μ = 0.539 mm-1, the final R = 0.0629 and wR = 0.1789 for 5298 observed reflections with I > 2σ(I). Compounds 1 and 2 are linear trinuclear and dinuclear manganese complexes respectively, which are both bridged by carboxylate groups of the ligands. Two manganese complexes [Mn3 (2-cba) 6 (phen) 2] 1 (2-cba = 2-cyanobenzoic acid, phen = 1,10-phenanthroline) and [Mn2 (PF6) 2 · 2H2O 2 (4-fbao = 4-formylbenzoic acid oxime), have been synthesized by the reaction of 2-formylbenzoic acid oxime (2-fbao, H2L1) or 4-formylbenzoic acid oxime ) with phen and manganese acetate in ethanol or methanol solution. A translation from the oximino (-CHN = OH) of H2L1 to cyano (-C≡N) was found in the formation of complex 1 at room temperature. The complexes were structurally determined The crystal of compound 1 belongs to monoclinic space group C2 / c with a = 17.983 (6), b = 23.364 (7), c = 14.589 (5) o V = 6124 (3) 3 Z = 4 C72H40Mn3N10O12 Mr = 1401.96 Dc = 1.521 g / cm3 F000 = 2852.0 Rint = 0.0372 T = 293 K = μ = 0.686 mm-1, the final R = 0.0644 and wR = 0.1813 for 5803 observed reflections with I> 2σ (I). The crystal of compound 2 is of monoclinic system, space group P21 / n with a = 13.050 (4) b = 20.577 (5) c = 13.323 (4) β β = 113.578 (3) o V = 3227.2 (14) 3 Z = 2 C64H48F12Mn2N10O8P2 , Mr = 1484.94, Dc = 1.528 g / cm3, F (000) = 1508.0, Rint = 0.0295, T = 293 (2) K, μ = 0.539 mm-1, the final R = 0.0629 and wR = 0.1789 for 5298 reflections with I> 2σ (I). Compounds 1 and 2 are linear trinuclear and dinuclear manganese complexes respectively, which are both bridged by carboxylate groups of the ligands.
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