The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuCl2, 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 deter- mined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P21/n with a = 8.2096(16), b = 18.580(4), c = 11.838(2) , β = 103.12(3)o, V = 1758.5(6) 3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm3, 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)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}] (phen = 1,10-phenanthroline, tp = terephthalate) 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P21/c with a = 13.1711(7), b = 19.6132(10), c = 13.6910(7) , β = 117.6870(10)°, V = 3131.8(3) 3, Z = 2, C64H44Cu4Mo4N8O24, Mr = 1946.99, Dc = 2.065 g/cm3, F(000) = 1920, μ(MoKα) = 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 complex fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bond- ing between adjacent layers further extends the compound into a 3-D framework.
A novel Cu(II)-2,2′-bipy-supported (bipy = bipyridine) mixed valence decatungstate, [Cu(2,2′-bipy)2]2Na2W6VW4VIO30·2H2O 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) , α = 80.631(10), β = 70.226(10), γ = 72.329(9)°, V = 1459.64(4) 3, Z = 1, Dc = 3.582 g/cm3, 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 CuII. 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) ,V=1916.5(7) 3,Z=8,Mr=318.57,Dc= 2.208 g/cm3,F(000)=1232 and μ=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,η2,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 tri- dentate ligand namely, N-(2-pyridylmethyl)-phenylalanine (Hpmpa), have been synthesized by hydrothermal reactions. [Zn(L-α-pmpa)2·H2O] 1: orthorhombic, space group P21212 with a = 15.1091(7), b = 16.2417(8), c = 5.9972(3) , V = 1471.70(12) 3, Z = 2, Mr = 593.97, Dc = 1.340 g/cm3, 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) , V = 1473.21(10) 3, Z = 2, Mr = 611.98, Dc = 1.380 g/cm3, 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) , β = 120.2210(10)o, V = 2693.66(7) 3, Z = 4, Mr = 575.95, Dc = 1.420 g/cm3, 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.
