By use of a new ligand containing both salicylic acid moiety and salicylaldehyde Schiff base moiety, 5-(2-hydroxybenzylideneamino)-2-hydroxybenzoic acid (H3L), a linear trinuclear Mn(II) complex was prepared. This complex crystallizes in triclinic, space group P1 with a = 12.0196(7), b = 13.7440(13), c = 15.7554(14) , α = 111.529(3), β = 96.691(2), γ = 94.802(2)o, C96H100Mn3N6O32, Mr = 2014.64, V = 2382.0(3) 3, Z = 1, μ = 0.478, Dc = 1.404 g/cm3, F(000) = 1049, R = 0.0554 and wR = 0.1610 for 8973 observed reflections (I > 2σ(I)). The complex consists of a trinuclear cluster and two solvate ethanol molecules. Three linearly disposed Mn atoms, with an inversion center on the central one, are bridged by six carboxylate groups from six bulky mono-anionic ligands (H2L–), and the octahedral coordination spheres for each of the metal centers are thus formed, with the aid of additional ligation of two small molecules (ethanol and water) to both ends. The magnetic properties of the title complex are also included in this paper.
A new manganese compound [Mn8(tmp)2(Htmp)4((CH3)3CCO2)4(py)2Cl2]·2py (1·2py, H3tmp = 1,1,1-tri(hydroxymethyl)propane, py = pyramid) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378(5), b = 14.334(5), c = 15.012(6) , α = 107.637(5), β = 95.635(3), γ = 92.825(4)°, V = 2720.7(17) 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F(000) = 1052, T = 293(2) K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections (I > 2σ(I)). X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles (Mn3), each of which is bridged by a μ3-oxygen atom.
Two diiron dithiolate complexes, (μ-pdt)Fe2(CO)5(C7H10N2) 3 and (μ-edt)-Fe2(CO)5(C7H10N2) 4 (pdt = -S(CH2)3S-, edt = -S(CH2)2S-), have been synthesized and characterized by single-crystal X-ray diffraction. Complex 3 crystallizes in the monoclinic system, space group P21/c with a = 10.168(4), b = 11.816(4), c = 16.595(7) and β = 95.195(6)o; and complex 4 crystallizes in the orthorhombic system, space group P212121 with a = 9.317(3), b = 11.898(4), c = 34.006(10) .The distances of Fe(1)–Fe(2) are 2.5058(9) in 3 and 2.4942(10) in 4, falling in the normal range of Fe–Fe bond length (2.49～2.57 ). The cyclic voltammograms show that 3 and 4 display irreversible reduction peaks (FeIFeI/ FeIFe0) at –1.717 V and –1.673 V vs. Ag/AgCl, respectively. With different acids, complex 3 has distinguishable behavior, two protonations in addition of HBF4-Et2O and single protonation besides HOAc-CH3CN, and complex 4 has a similar action to 3 with HOAc-CH3CN for a semblable structure.
