The two title complexes, [Cd{3,5-(NO2)2sal}(2,2′-bipy)]n 1 and [Mn{3,5- (NO2)2sal}(2,2′-bipy)]n 2 (3,5-(NO2)2sal = 3,5-dinitrosalicylate, 2,2'-bipy = 2,2′-bipyridine), were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic, space group P1, a = 5.581(4), b = 12.071(8), c = 12.88(1)A, α= 92.10(3),β= 96.73(3), γ = 102.02(2)°, C17H10N407Cd, Mr = 494.69, V= 841(1)A3, Z = 2, Dc = 1.954 g/cm3, F(000) = 488, μ= 1.353 mm^-1, R = 0.0248 and wR = 0.0761. Complex 2 crystallizes in monoclinic with space group P21/c, a = 8.604(3), b = 23.88(1), c = 8.894(3) A, β = 102.45(1)°, C17H10N407Mn, Mr = 437.23, V= 1785(1) A3, Z=.4, Dc = 1.627 g/cm3, F(000) = 884, μ = 0.791 mm^-1, R = 0.0471 and wR = 0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units (Cd2O2) and eight-membered ring units (CdOCO)2. Compound 2displays a linear 1D chain through Mn(Ⅱ) atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472(2)A. The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.
The copper complex Cu(C12H9N2O3)2 has been synthesized by the reaction of furaldehyde salicylylhydrazone (Hfs) and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P211n with a = 5.9765(3), b = 15.7196(9), c = 12.0514(6)A,β= 101.618(3)^o, V = 1109.0(1)A^3, C24H18CuN4O6, Mr = 521.96, Z = 2, Dc = 1.563 g/cm^3, μ = 1.035 mm^-1, F(000) = 534, R = 0.0373 and wR = 0.1058 for 2283 observed reflections (I 〉 2σ(I)). The copper atom has a square-planar CuN2O2 coordination and should be in an octahedral coordination if considering Cu-O (phenol) with distances of 2.796(2)A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O (phenol) bonds, resulting in an extended 1D chain. The title compound exhibits paramagnetic property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.
Two complexes, Cu(HnicO)2 1 and Ni(HnicO)2(H2O)2 2 (H2nicO = 2-hydroxynicolinic acid), were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in monoclinic, space group P21/n, with a = 8.314(7), b = 6.275(4), c = 11.283(7)A, β = 98.32(3)°, V = 582.5(7)A^3, Z = 2, Mr = 339.74, Dc = 1.937 g/cm3, F(000) = 342, μ = 1.908 mm^-1, S = 1.097, the final R = 0.0284 mad wR = 0.0781 for 1177 observed reflections with Ⅰ 〉 2σ(Ⅰ). Complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.438(5), b = 12.22(1), c = 7.537(5)A,β = 100.07(3)°, V= 674.3(8)A3, Z = 2, Mr = 370.95, Dc = 1.827 g/cm^3, F(000) = 380, = 1.487 mm^-1, S = 1.041, the final R = 0.0335 and wR = 0.0779 for 1202 observed reflections with I 〉 2σ(Ⅰ). There are extended 3D framework structures in complexes 1 and 2 due to the N-H…O and C-H…O hydrogen bonds. The copper atom in 1 has square planar coordination, while the nickel atom in 2 adopts octahedral coordination geometry. The TG curve shows that complex 2 is stable in solid state to 150 ℃.