Synthesis and Crystal Structure of Bis(dicyanamide)(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane) Nickel(Ⅱ)

The nickel ( Ⅱ ) complex [Ni(teta) { N(CN)2 } 2] (teta = 5,7,7,12, 1 4, 1 4-hexamehyl- 1,4,8,1 1-tetraazacyclotetradecane) was synthesized and its structure has been determined by singlecrystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) A, β= 93.46(3)°, V= 1207.4(4) A3, Mr = 475.30, Z= 2, Dc= 1.307 g/cm3,F(000) = 508,μ(MoKα) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I ＞ 2σ(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.     

Synthesis and Crystal Structure of an Ion-pair Compound:[H2(teta)]2+·[Ni(CN)4]2-·2H2O(teta=Meso-5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane)

The ion-pair compound [H2(teta)]2+·[Ni(CN)4] 2-·2H2O (C20H42N8NiO2, teta = meso- 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) was synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 10.0784(10), b = 9.5411(7), c = 14.1010(14)(A), β= 106.752(2)o, V = 1298.4(2) (A)3, Mr = 485.33, Z = 2, Dc = 1.241 g/cm3,μ(MoKα) = 0.778 mm-1 and F(000) = 524. The structure was refined to R = 0.0391 and wR = 0.0870 for 2614 observed reflections with I > 2σ(I). The title compound contains one [Ni(CN)4]2- anion, one protonated macrocyclic tetraamine cation [H2(teta)]2+ and two water molecules. There are multiform hydrogen bonds in the compound to link the different components and stabilize the crystal structure.     

Synthesis, Structure and Luminescent Properties of Polymeric Copper(Ⅰ) Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

Three polymeric copper(Ⅰ) halide complexes bearing phosphine and N-donor bridging ligands, [(PPh3)2Cu2(μ-Br)2(μ-4,4'-bipy)]∞ 1 (bipy=bipyridine), [(PPh3)2Cu2(μ-Br)2(μ-bpe)]∞ 2 (bpe=trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P-1 with a=9.122(3), b=9.322(3), c=13.201(4) (A),α=106.440(4), β=105.965(5), γ=94.167(5)°, V=1021.3(6) (A), Mr=967.62, Z=1,Dc=1.573 g/cm3, F(000)=486,μ=3.111 mm-1, the final R=0.0383 and wR=0.0960 for 2792observed reflections (I ＞ 2σ(Ⅰ)). Complex 2 crystallizes in triclinic, space group P-1 with a=9.420(3), b=10.209(4), c=12.407(4)(A), α=104.136(6), β=108.132(5), γ=95.338(6)°, V=1081.0(7)(A), Mr=496.83, Z=2, Dc=1.526 g/cm3, F(000)=500,μ=2.941 mm-1, the final R=0.0445 and wR=0.1117 for 3251 observed reflections (I＞ 2σ(Ⅰ)). Complex 3 crystallizes in triclinic,space group P-1 with a=8.32(1), b=11.53(2), c=13.94(3)(A), α=109.57(3), β=93.85(3), γ=97.28(3)°, V=1242(4)(A)3, Mr=1074.59, Z=1, Dc=1.436 g/cm3, F(000)=548,μ=1.279 mm-1,the final R=0.0786 and wR=0.1586 for 2266 observed reflections (I ＞ 2σ(Ⅰ)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.     

Conformation Diversity of Complexes Constructed by N-（2-Pyridylmethyl）-phenylalanine and Zn（Ⅱ）

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.     

Syntheses and Crystal Structures of Four Cobalt Supramolecular Architectures with Hmtyaa Ligand

Four cobalt supramolecular architectures with Hmtyaa(2-(5-methyl-1,3,4-thiadiazol-2-ylthio)acetic acid) ligand have been synthesized.[Co(mtyaa)2(H2O)4]·4(H2O)(1):triclinic,space group P1 with a = 6.7537(18),b = 8.591(2),c = 10.615(3) ,α = 96.495(4),β = 99.955(5),γ = 103.615(5)°,V = 581.9(3) 3,Z = 1,Mr = 581.52,Dc = 1.659 g/m3,μ = 1.158 mm-1,F(000) = 301,Rint = 0.0557,R = 0.0377 and wR = 0.1056 for 1854 observed reflections with Ⅰ 2σ(Ⅰ);{[Co(4,4'-bipy)(H2O)4]·2(mtyaa)·2(H2O)}n(2):triclinic,space group P1 with a = 7.669(2),b = 8.840(3),c = 11.521(4) ,α = 79.912(5),β = 73.954(5),γ = 86.612(6)°,V = 738.9(4) 3,Z = 1,Mr = 701.67,Dc = 1.577 g/m3,μ = 0.924 mm-1,F(000) = 363,Rint = 0.0636,R = 0.0498 and wR = 0.1311 for 2155 observed reflections with Ⅰ 2σ(Ⅰ);{[Co(4,4'-bipy)(mtyaa)(H2O)3](mtyaa)·2(H2O)}(3):monoclinic,space group Pc with a = 7.7832(17),b = 11.527(3),c = 31.483(7) ,β = 91.952(4)°,V = 2822.9(11) 3,Z = 4,Mr = 683.65,Dc = 1.609 g/m3,μ = 0.963 mm-1,F(000) = 1412,Rint = 0.0758,R = 0.0609 and wR = 0.1095 for 5841 observed reflections with I 2σ(I);{[Co(bpe)(mtyaa)2(H2O)2]}n(4):monoclinic,space group C2/c with a = 19.290(11),b = 12.027(7),c = 14.865(8) ,β = 125.648(8)°,V = 2802(3)3,Z = 4,Mr = 657.66,Dc = 1.559 g/m3,μ = 0.959 mm-1,F(000) = 1356,Rint = 0.0456,R = 0.0332 and wR = 0.0985 for 2299 observed reflections with Ⅰ 2σ(Ⅰ).     

Syntheses and Crystal Structures of Two Silver(I) Complexes Isolated by the Reaction of [Ag(PPh3)2(MeCN)](SbF6) with a N6 Ligand

1 INTRODUCTION The polyaza macrocyclic and macrobicyclic mo-lecules have been extensively studied due to theirinclusion ability for neutral molecules, coordinationability for metal cations and versatile roles in thefields of recognition, transformation…     

Syntheses and Crystal Structures of Mono- and Binuclear Copper( Ⅱ ) Mixed-ligand Complexes Involving Schiff Base

The mononuclear copper(Ⅱ) complex [Cu(L)(2-AP)] 1 and binuclear copper(Ⅱ)complex [Cu(L)(py)]2 2 (L = C1oH1 1O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine)with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1: orthorhombic, space group Pbca with a = 11.921(4), b = 15.816(6), c = 17.076(6) (A), V=3219.7(19) (A)3, C15H17CuN3O5S, Z = 8, Mr = 414.92, Dc = 1.712 g/cm3,μ(MoKα) = 1.520 mm-1,F(000) = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I ＞ 2σ(I);and crystal data for 2: monoclinic, space group P21/c with a = 7.929(3), b = 17.038(5), c = 11.734(4)(A), β = 98.162(6)°, V = 1569.1 (9) (A)3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm3, F(000)= 820,μ(MoKα) = 1.554 mm-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections (I ＞ 2o(I)). The molecular structure of complex 1 consists of one tetra-coordinated Cu(Ⅱ) atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper(Ⅱ) structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.     

Synthesis and Crystal Structure of 2-（ 4-Decarboxydehydroabietyl）- 5-p-tolyl-[ 1,3,4 ]-oxadiazole

2-（4-Decarboxydehydroabietyl）-5-p-toyl-[1,3,4]-oxadiazole, C28H34N2O, has been synthesized and characterized by IR, NMR, elemental analysis and single-crystal X-ray diffraction method. The crystal belongs to the orthorhombic system, space group P212121 with a = 6.1351（5）, b = 14.8495（19）, c = 25.9050（2） A, V = 2360.0（4） A3, Z = 4, Mr = 414.57, Dc = 1.167 Mg/m^3, 2 = 0.71073 A,μ（MoKa） = 0.070 mm^-1, F（000） = 896, the final R = 0.0452 and wR = 0.1076 for 1647 observed reflections with I 〉 2σ（I）. There are five rings in the crystal structure of the title compound, but the oxadiazole ring is non-coplanar with the benzene ring D.     

Molecular and Supramolecular Structures of Manganese(Ⅱ) and Cobalt(Ⅱ) Complexes with 1-Carboxymethylpyridinium-4-carboxylate

Two complexes with a zwitterionic dicarboxylate ligand,Mn(L)2(H2O)4 1 and Co(L)2(H2O)4 2(L = 1-carboxymethylpyridinium-4-carboxylate),were synthesized and structurally characterized.Complex 1 crystallizes in monoclinic,space group P21 with a = 6.490(2),b = 19.210(7),c = 7.813(3) ,β = 92.716(5)o,V = 972.9(6) 3,Z = 2,Mr = 487.28,Dc = 1.663 g/cm3,F(000) = 502,μ = 0.749 mm-1,S = 1.060,the final R = 0.0377 and wR = 0.0893 for 3292 observed reflections with I 2σ(I).Complex 2 is isomorphous with 1,with a = 6.478(2),b = 19.052(7),c = 7.742(3) ,β = 92.690(4)o,V = 954.6(6) 3,Z = 2,Mr = 491.28,Dc = 1.709 g/cm3,F(000) = 506,μ = 0.971 mm-1,S = 1.035,the final R = 0.0425 and wR = 0.0809 for 3289 observed reflections with I 2σ(I).In the compounds,the mononuclear [M(L)2(H2O)4] units with trans-octahedral coordination geometry are linked into 3D architectures via hydrogen bonding(or second-sphere coordination) involving carboxylate groups and coordinated water molecules.The 3D networks illustrate a 3,8-connected net with Schlfli symbol(4·62)2(42·623·83).     

Synthesis and Crystal Structure of Bis(dicyanamide) (5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane) Nickel(Ⅱ)

1 INTRODUCTION Crystal engineering is becoming an increase- ingly interest field by means of coordinated co- valent bonding or supramolecular contacts (such as hydrogen bonds, p-p interaction etc.)[1～7]. The ligand [N(CN)2]- is a remarkably versatile building block for constructing supramolecular architectures since it may act in uni-, biand tridentate manner. Additional ligands, such as coordinating amines (Lewis bases), in combination with dicyan- amide have been shown to produce n…     

From Chain to Layer Structure: ZnⅡ Coordination Polymers Derived from Diphenic Acid

Three ZnⅡ coordination polymers, [Zn(py)(H2O)(dpa)]n 1, [Zn2(4,4'-bipy)2(dpa)2]n 2 and [Zn(bpe)(H2O)2(Hdpa)2]n 3 (py = pyridine, H2dpa = diphenic acid, 4,4'-bipy = 4,4'-bipyridine,bpe = 1,2-bis(4-pyridyl)ethane), were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in monoclinic, space group C2/c with a = 23.014(3), b = 8.7184(13), c = 18.091(3) (A), β = 95.964(3)°, V = 3610.2(9) (A)3, Z = 8, C19H15NO5Zn, Mr = 402.69,Dc= 1.482 g/cm3, F(000) = 1648, μ(MoKα) = 1.389 mm-1, the final R = 0.0431 and wR = 0.1120 for 4239 observed reflections with I ＞ 2σ(Ⅰ). 2 crystallizes in orthorhombic, space group Fddd with a = 23.1613(5), b = 24.0324(6), c = 29.4785(1) (A), V= 16408.4(5) (A)3, Z = 32, C24H16N2O4Zn, Mr = 461.76, Dc= 1.495 g/cm3, F(000) = 7552, μ(MoKα) = 1.232 mm-1, the final R = 0.0542 and wR = 0.1724 for 3632 observed reflections with I ＞ 2σ(Ⅰ). 3 crystallizes in orthorhombic, space group C2/c with a = 19.142(4), b = 13.862(3), c = 15.625(3) (A), β = 122.404(3)°, V = 3500.3(11) (A)3, Z = 8,C20H17NO5Zn0.50, Mr = 384.03, Dc= 1.457 g/cm3, F(000) = 1592,μ(MoKα) = 0.766 mm-1, the final R = 0.0400 and wR = 0.1210 for 4024 observed reflections with I ＞ 2σ(Ⅰ).     

Ionothermal Syntheses and Crystal Structures of Two Cobalt（Ⅱ） Compounds：Co（2,2＇-bpy）_2Br_2 and Co（1,10-phen）_2Br_2

Two cobalt(Ⅱ) compounds,Co(2,2-bpy) 2 Br 2 (1,2,2-bpy=2,2-bipyridyl) and Co(1,10-phen) 2 Br 2 (2,1,10-phen=1,10-phenanthroline),have been prepared under ionothermal reactions using the 1-propyl-3-methylimidazolium bromide ionic liquid solvent.Single-crystal X-ray analyses reveal that 1 crystallizes in a monoclinic space group P2 1 /c,with a=8.5509(13),b=14.804(2),c=15.650(2),β=97.119(2) o,V=1965.8(5) 3,Z=4,C 20 H 16 Br 2 N 4 Co,M r=531.12,D c=1.795 g/cm 3,μ=4.950 mm-1,F(000)=1044,the final R=0.0467 and wR=0.0736 for 2291 observed reflections with I > 2σ(Ⅰ).Complex 2 crystallizes in a monoclinic space group P2 1 /n,with a=10.4237(8),b=16.8657(12),c=12.4945(9)b,β=102.110(1) o,V=2147.7(3) 3,Z=4,C 24 H 16 Br 2 N 4 Co,M r=579.16,D c=1.791 g/cm 3,μ=4.540 mm-1,F(000)=1140,the final R=0.0431 and wR=0.1042 for 3470 observed reflections with I > 2σ(Ⅰ).The mononuclear molecules of 1 are linked by the C-H···Br hydrogen bonds and π-π interactions to form a three-dimensional supramolecular framework structure.The C-H···Br hydrogen bonds and π-π interactions link the mononuclear molecules of 2 to give a two-dimensional layer structure.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

以联吡啶二羧酸及邻菲咯啉衍生物为配体的两种锌(Ⅱ)配合物的水热合成及晶体结构

在水热条件下合成了两种配合物[Zn(bpdc)(pyip)2].3H2O(1)和[Zn(pip)2(Hpip)].3H2O(2)(H2bpdc=2,2′-联吡啶-3,3′-二羧酸,pyip=2-(3-吡啶基)-1H-咪唑并[4,5-f][1,10]邻菲咯啉,Hpip=2-苯基-1H-咪唑并[4,5-f][1,10]邻菲咯啉),并利用红外和X射线单晶衍射对其结构进行了表征。配合物1属单斜晶系,P21/c空间群,晶胞参数a=1.656 9(5)nm,b=1.3614(4)nm,c=1.863 7(6)nm,β=93.128(6)°,V=4.198(2)nm3,Z=4,ZnC48H34N12O7,Mr=955.99,Dc=1.513 g.cm-3,μ(Mo Kα)=0.657 mm-1,F(000)=1 968,GOOF=1.008,R=0.057 7,wR=0.107 5,其中4 622个可观测衍生点(I>2σ(I))。配合物2属单斜晶系,P21/c空间群,晶胞参数a=1.797 7(4)nm,b=1.527 0(3)nm,c=1.767 6(4)nm,β=102.84(3)°,V=4.730 9(19)nm3,Z=4,ZnC57H40N12O3,Mr=1 006.36,Dc=1.410 g.cm-3,μ(Mo Kα)=0.581mm-1,F(000)=2 072,GOOF=1.134,R=0.089 5,wR=0.208 4,其中6 558个可观测衍射点(I>2σ(I))。结构分析表明配合物1和2均为零维结构,氢键和π-π相互作用在加固配合物的结构中起到重要作用。此外,对化合物的热稳定性和荧光性质也进行了研究。     

Synthesis and Crystal Structure of Chiral 4-Hydroxy-4-butyrolactam Fused Aziridine

A novel compound of chiral 4-hydroxy-4-butyrolactam fused aziridine was synthesized via tandem nucleophilic displacement reaction under mild condition. Its structure was determined by IR, 1H NMR, elemental analysis and X-ray diffraction. The crystal of the new compound is of orthorhombic, space group P212121 with a = 6.4246（6）, b = 13.5081（13）, c = 18.6399（18） A, Mr = 278.39, Z = 4, V = 1617.6（3）A^3, Dc = 1.143 g/cm^3, p（MoKa） = 0.075 mm^-1, F（000） = 608, the final R = 0.0297 and wR = 0.0679.     

Hydrothermal Synthesis and Crystal Structure of a Novel Composite Keggin-type Arsenotungstate： [Ni（phen）2] [Hphen] （AsW12O40）

A novel polyoxometalate-based composite compound [Ni(phen)2][Hphen](AsW12O40) (phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, ESR spectroscopy and single-crystal X-ray diffraction. Each structure unit of 1 consists of one polyoxoanion AsW12O403-, one free phenanthroline molecule and one coordination cation [Ni(phen)2]2+. The title compound crystallizes in the orthorhombic system, space group P212121, with a = 12.2383(7), b = 21.0884(11), c = 22.3237(12) , V = 5761.4(5) 3, Mr = 3520.44, Z = 4, Dc = 4.059 g/cm3, F(000) = 6204, μ(MoKα) = 24.844 mm-1, GOF = 1.022, the final R = 0.0376 and wR = 0.0742 (I > 2σ(I)) for 865 parameters and 9637 observed reflections with I > 2σ(I).     

Synthesis and Characterization of Two Chiral Cadmium Coordination Compounds Constructed from (1S,1′S)-1,1′-(4-amino-4H-1,2,4-triazole-3,5-diyl)diethanol

Two chiral cadmium coordination compounds,(S)-[Cd(deoatrz)2 Cl2](1)and(S)[Cd(deoatrz)2 (NO3)2](2)(deoatrz=(1S,1 S)-1,1-(4-amino-4H-1,2,4-triazole-3,5-diyl)diethanol),are reported.Both 1 and 2 are mononuclear,crystallizing in tetragonal P41212 chiral space group with Z=2.For1,a=11.520(3),b=11.520(3),c=15.175(1),V=2013.6(1)3,Mr=527.7,Dc =1.741 g/cm 3,μ=1.386mm-1,F(000)=1064,the final GOF=1.05,R=0.0147 and wR=0.0433 for1932 observed reflections with I>2σ(I).For 2,a=12.201(3),b=12.201(3),c=15.027(4),V=2237.1(1)3,Mr=580.8,Dc=1.725 g/cm 3,μ=1.047mm-1,F(000)=1176,the final GOF=1.00,R=0.0201 and wR=0.0415 for 2408 observed reflections with I>2σ(I).Compounds 1 and 2 are connected into three-dimensional supramolecular networks through hydrogen bonding interactions.     

Synthesis, Crystal Structure and Properties of a Novel Tetranuclear Nickel（II） Complex with Azo-enolic-2-hydroxybenzamide

A novel tetranuclear nickel(Ⅱ) complex [Ni4L2(DMF)2(H2O)2·2DMF] (1,H4L=azo-enolic-2-hydroxybenzamide, DMF=N,N-dimethyl-formamide) has been synthesized and characterized by elemental analysis, UV, IR and X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P21/n with a=8.8944(11), b=14.4583(18), c=18.097(2) , β=90.00(2)o, Z=2 , V=2327.2(5)3 , C40H48N12Ni4O14 , Mr=1155.66, Dc=1.649g/cm 3 , μ=1.672 mm-1 , F(000)=1192, R=0.0392 and wR=0.0958. The local coordination environment around the nickel ions exist a distorted octahedral and quadrangle geometry in the molecular structure. Complex 1 exhibits strong photoluminescent emission in the ultraviolet region at room temperature. The electrochemical studies reveal that redox of Ni 3+ /Ni 2+ in the complex is a quasi-reversible process.     

Two Metal-organic Frameworks（MOFs） Assembled from One Asymmetric Semirigid Multicarboxylate Ligand：Syntheses and Crystal Structural Characterizations

Hydrothermal reactions between a new flexible multicarboxylate ligand of 3-(2-carboxy-phenoxy)-benzoic acid(H2L) and transitional metal cations of M2+(M = Cu2+,Ni2+) in the presence of the secondary ligands of 1,10-phenanthroline(phen),2,2'-bipyridine(2,2?-bpy),and 4,4'-bipyridine(4,4'-bpy) afford two novel coordination polymers Ni2(H2O)2L2(phen)(μ-4,4'-bpy)(1) and CuIIL(2,2'-bpy)(2).Both compounds were characterized by X-ray crystallography.Crystal data of 1:C31H24N3NiO7,Mr = 609.24,monoclinic,space group P21/c,a = 17.560(8),b = 10.528(5),c = 30.613(15) ,V = 5659(5) 3,Z = 4,Dc = 1.430 g/cm3,F(000) = 502,μ = 0.739 mm-1,R = 0.0902,wR = 0.1346(I > 2σ(I)),S = 1.002.Crystal data of 2:C24H16CuN2O5,Mr = 475.93,monoclinic,space group P21/n,a = 9.8904(13),b = 11.0782(16),c = 18.321(3) ,β = 11.0782(16)°,V = 1993.8(5) 3,Z = 4,Dc = 1.585 g/cm3,F(000) = 972,μ = 1.137 mm-1,R = 0.0433,wR = 0.0723(I > 2σ(I)) and S = 1.004.Compound 1 displays a one-dimensional(1D) zigzag chain structure constructed from phen ligands and the deprotonated ligands of L2-,which further forms a ladder-shaped supramolecular architecture via the bridge of 4,4'-bpy ligand.Complex 2 also possesses a ladder-shaped architecture based on the dinuclear CuII units.     

Synthesis,Structure,Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[Cd[μ-(4,4'-dps) ]2(H2O)2]·(4-abs )2(H2O)2}n

A new cadmium(Ⅱ) compound,{[Cd[μ-(4,4'-dps) ]2(H2O)2]·(4-abs )2(H2O)2}n1(4,4'-dps=4,4'-dipyridylsulfide,4-abs=deprotonated 4-amino benzenesulfonic acid),has been synthesized and structurally characterized.It belongs to the orthorhombic system,space group Pbcn with a=19.950(3),b=10.6381(13),c=18.055(2) A,V=3831.8(8) A3,Z=4,C32H36CdN6O10S4,Mr=905.31,F(000)=1848,μ=0.850 mm-1,Dc=1.569 Mg/m3,the final R=0.0238 and wR=0.0589 for 3080 observed reflections with I > 2σ(I).Complex 1 is a one-dimensional linear chain coordination polymer and the repeat unit is comprised of doubly charged cadmium complex cation,uncoordinated 4-aminobenzene sulfonate anions and water molecules.The cadmium(Ⅱ) ion adopts a six-coordinate distorted octahedral geometry.Complex 1 is stabilized and linked into a three-dimensional layered structure through intermolecular O-H…O and N-H…O hydrogen bonds together with electrostatic force.The cyclic voltammograms and fluorescence spectrum of 1 were also measured.It shows one irreversible redox process and emits a very strong and sharp fluorescent band at about 341 nm.