A new one-dimensional (1-D) Zn(Ⅱ) nitronyl nitroxide complex bridged by pyridine-2,4-dicarboxylate anion, [Zn(NIT4Py)(2,4-PDA)(H2O)2], (NIT4Py = 2-(4′-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide and 2,4-PDA = pyridine-2,4-dicarboxylate anion), has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 16.834(2), b = 7.4376(10), c = 18.295(3) A, β = 102.848(2)°, V = 2233.2(5) A^3, C19H23N4O3Zn, Mr = 500.78, Dc = 1.489 g/cm^3,μ(MoKa) = 1.152 mm^-1, F(000) = 1036, Z = 4, the final R = 0.0390 and wR = 0.0915 for 3234 observed reflections. In the complex, each zinc(Ⅱ) ion is six-coordinated by one nitrogen atom of the radical ligand (NIT4Py), one nitrogen atom and two oxygen atoms of two 2,4-PDA anions and two oxygen atoms of two water molecules. Each 2,4-PDA anion bridges two Zn(Ⅱ) ions via a tridentate mode into a 1-D chain, and these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.
Two novel complexes {[Zn(IM4py)2(tp)(H2O)]2H2O}. 1 and {[Cd(IM4py)2(tp)- (H2O)]1.25H2O},, 2 (IM4py = 2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-l-oxyl and tp = terephthalate dianion) have been synthesized and characterized by elemental analyses, IR spectrum and single-crystal X-ray diffraction. Crystal data for complex I: monoclinic, space group C2/c, a = 20.648(7), b = 12.130(4), c = 14.036(4) A, β = 106.351(5)°, C32H42N6O9Zn, Mr = 720.09, V = 3373.3(2) A3, Z= 4, Dc = 1.418 g/cm^3μt(MoKα) = 0.790 mm^-1, F(000) = 1512, the final R = 0.0407 and wR = 0.0894 for 3480 independent reflections with Rint = 0.0432. Crystal data for complex 2: monoclinic, space group C2/c, a = 21.332(6), b = 12.063(3), c = 14.246(4) A, β = 106.704(4)°, C32H40.50N6O8.25Cd, Mr = 753.60, V= 3511.2(2) A^3, Z = 4, Dc = 1.426 g/cm^3,μ(MoKα) = 0.679 mm^--1, F(000) = 1554, the final R = 0.0419 and wR = 0.0961 for 3627 independent reflections with Rint = 0.0440. The framework structures of complexes 1 and 2 are 3-D networks via the hydrogen bonds among 1-D chains. The notable characteristics of the two complexes are that the coordination polyhedron of Zn(Ⅱ) adopts a rare distorted five-coordinate square pyramidal geometry in 1, and the Cd(Ⅱ) complex exhibits an unusual distorted seven-coordinate pentagonal bipyramid in 2.