The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuC12, 2,2＇-bipyridine and H2O affords a novel dinuclear copper（Ⅱ）-ditetrazolate, [Cu（bpy）- （pdtz）]2 （Hpdtz = 5,5＂-1,2-phenylene-ditetrazole, bpy = 2,2＇-bipyridine）. The pdtz ligand is generated in situ through Sharpless 2＋3 cycloaddition reaction. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P211n with a = 8.2096（16）, b = 18.580（4）, c = 11.838（2） A, β = 103.12（3）°, V = 1758.5（6） A^3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm^3, F（000） = 876 and μ = 1.272 mm^-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.
HUANG Xi-He SHENG Tian-Lu XIANG Sheng-Chang FU Rui-Biao HU Sheng-Min LI Ya-Min WU Xin-Tao
Hydrothermal reaction of 1,2,4-benzenetricarboxylic acid, and MnCl24H2O with 1,10-phenanthroline gave the title complex, [Mn(phen)(m-phth)]n, which crystallizes in the monoclinic system, space group P2/c with a=0.83582(3) nm, b=1.04246(4) nm, c=1.87777(7) nm, =100.314(2), V=1.60968(10) nm3, Z=4, and the final R=0.0576, wR=0.1294. In the complex, each Mn(II) ion is coordinated to four O atoms of carboxylate groups and two N atoms of phen. Isophthalate was generated in situ through the loss of one carboxylate group of 1,2,4-benzenetricarboxylic acid under the hydrothermal condition. Each isophthalate is bound to three manganese atoms through O atoms of carboxylate in bridging and chelating fashion, affording manganese(II) pairs that are linked by the isophthalate group to yield a zig-zag chain along the c-axis.
A novel copper molybdate with mixed ligands, [{（Cu·phen）e（tp）} {（Cu·phen·H2O）2（tp）} {Mo4O14}（phen = 1,10-phcnanthroline, tp = tercphthalate） 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P2l/c with a = 13.1711（7）, b = 19.6132（10）, c= 13.6910（7） A, β = 117.6870（10）°, V= 3131.8（3） A^3, Z= 2, C64H44Cu4MoaN8O24, Mr= 1946.99, D, = 2.065 g/cm^3, F（000） = 1920,μ（MoKa） = 2.198 mm ^1, R = 0.0810 and wR = 0.2012 for 4233 observed reflections （I 〉 2σ（I））. The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper colnplcx fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bonding between adjacent layers further extends the COlnpound into a 3-D framework.
A novel Cu（II）-2,2＇-bipy-supported （bipy = bipyridine） mixed valence decatungstate, [Cu（2,2＇-bipy）2]2Na2W6^VW4^VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crystal of 1 is of triclinic, space group P1^- with a= 10.9393（10）, b = 12.0492（2）, c = 12.3783（2）A, a = 80.631（10）, β= 70.226（10）, γ= 72.329（9）^o, V = 1459.64（4）A^3, Z = 1, Dc = 3.582 g/cm^3, F（000） = 1404, R = 0.0553 and wR = 0.1242 for 4607 observed reflections （I 〉 2σ（I））. The EPR spectrum of 1 indicates that its unpaired electrons are placed in the dx2-y2 orbital of the ground state of Cun. Furthermore, compound 1 shows an antiferromagnetic interaction.
A new compound, (H3O)3{Na3(H2O)13(Cu(Gly)2)2(H2W12O42)}·11H2O (1), has been synthesized and structurally characterized, which represents the first example of a polyoxotungstate-surface being decorated with amino acid ligand. Two cis-{Cu(Gly)2}2+ engraft into the (H2W12O42)10- with Cu-O bond of 0.241 2(7) nm, and Na+ ions linked these (Cu(Gly)2)2(H2W12O42)6- clusters into a one-dimensional chain. CCDC: 278000.
The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of Cd（NO3）2 affords a novel 2D cadmium tetrazolyl-benzoate, {Cd（tzbz）（H2O）}n （H2tzbz is 2-（5-tetrazolyl）-benzoate）. The tzbz ligand is generated in situ through the [2＋3] Sharpless cycloaddition reaction and hydrolyzation. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 9.6659（19）, b = 7.6366（15）, c = 25.964（5）A, V= 1916.5（7）A^3, Z= 8, Mr = 318.57, Dc = 2.208 g/cm^3, F（000） = 1232 and p = 2.276 mm^-1. The Cd（Ⅱ） atom is coordinated by four tzbz ligands and one water molecule to form a severely distorted pentangle bipyramid. While each tzbz ligand connects to four Cd（Ⅱ） atoms in a μ4-η1, η, η1, η1, η1 coordination mode to construct a 2D architecture of the title complex. Additionally, the title complex exhibits strong fluorescence at room temperature in the solid state.
HUANG Xi-He SHENG Tian-Lu XIANG Sheng-Chang FU Rui-Biao HU Sheng-Min LI Ya-Min WU Xin-Tao
＜正＞Crystal engineering of metal complexes,especially coordination polymers has been greatly developed in the p...
Shan-Ci Chen Xiao-Yuan Wu Zhen-Guo Zhao Can-Zhong Lu~* The State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China.
＜正＞Exploitation of polyoxometalates（POMs）as building blocks to construct organic-inorganic hybrid materials ha...
Xiao-Yuan Wu Can-Zhong Lu~* The State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China.
Four configurationally and conformationally related Zn（II） complexes with a tridentate ligand namely, N-（2-pyridylmethyl）-phenylalanine （Hpmpa）, have been synthesized by hydrothermal reactions. [Zn（L-α-pmpa）2·HaO] 1： orthorhombic, space group P21212 with a = 15.1091（7）, b = 16.2417（8）, c = 5.9972（3） A, V= 1471.70（12）A^3, Z = 2, Mr = 593.97, Dc = 1.340 g/cm^3,μ = 0.879 mm^-1, F（000） = 620, Rint= 0.0205, R = 0.0450 and wR = 0.1578 for 3102 observed reflections with I 〉 2σ（I）; [Zn（D-α-pmpa）2·2H2O] 2： orthorhombic, space group P21212 with a = 15.1023（6）, b = 16.2516（7）, c = 6.0024（2）A, V= 1473.21（10）A^3, Z = 2, Mr = 611.98, Dc = 1.380 g/cm^3,μ = 0.882 mm^-1, F（000） = 640, Rint= 0.0337, R = 0.0484 and wR = 0.1435 for 2408 observed reflections with I 〉 2σ（I）; [Zn（L-β-pmpa）2] 3： monoclinic, space group C2/c with a = 27.8667（5）, b = 5.60350（10）, c = 19.9636（2）A β = 120：2210（10）°, V = 2693.66（7）A^3, Z = 4, Mr = 575.95, De= 1.420 g/cm^3,μ = 0.955 mm^-1, F（000） = 1200, Rint= 0.0345, R = 0.0358 and wR = 0.1135 for 2251 observed reflections with I 〉 2σ（I）; and [Zn（D-β-pmpa）2] 4. They are all mononuclear discrete structures. The influence of temperature and pH on the conformation of structures has been investigated. Moreover, the photoluminescent properties of compounds 1 and 3 are also reported.
