Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C_(13)H_9N_2O)Cl]_2·(CH_3CN)_2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu(C13H9N2O)Cl]2·(CH3CN)2 (C30H24Cl2Cu2N6O2), has been synthesized and characterized by X-ray structure determination. It crystallizes in the tricli- nic system, space group P1, with a = 7.6677(14), b = 9.2375(17), c = 11.227(2) , α = 81.338(3), β = 88.173(4), γ = 66.199(3)o, V = 718.9(2) 3, Z = 1, Mr = 698.53, F(000) = 354, Dc = 1.613 g/cm3, μ(MoKα) = 1.705 mm-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms (one nitrogen atom, two oxygen anions, and one chlorine atom). Two copper(II) atoms are bridged by two oxygen anions (O(1) and O(1a)) of two phenolates to form a Cu(II)–Cu(II) binuclear entity, and the distance between two copper(II) atoms is 3.0144(15) .     

Synthesis,Crystal Structure and Property of a Binuclear Copper Complex [Cu_2L_2(pht)_2]_2·H_2O

A new binuclear copper complex, [Cu2L2(pht)2]2·H2O(Hpht = 5,5-diphenylhydantoin, i.e. phenytoin; L = 2-diethylaminoethanol), has been synthesized by the solvothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 31.918(3), b = 12.9222(15), c = 19.868(2) , β = 98.762(2)o, V = 8098.8(16) 3, Dc = 1.429 Mg/m3, Z = 4, F(000) = 3640, μ = 1.107 mm-1, R = 0.0560 and wR = 0.1276(I 2(I)). Each copper(Ⅱ) in a molecule is coordinated with N and O atoms from ligand L and N atom from ligand Hpht in a tetradentate manner. Moreover, two copper(Ⅱ) centers are bridged by two O atoms of hydroxyl groups from two L ligands to form a slightly distorted binuclear {Cu2O2} diamond configuration. In addition, the interaction of this complex with calf thymus DNA(CT-DNA) was investigated by UV-vis spectrum and viscometry, and the complex may bind to DNA through intercalation.     

Synthesis and Crystal Structure of the Binuclear Complex:[Cu_2(phen)_2(ip)(Hip)_2]·4H_2O

A binuclear complex [Cu2(phen)2(ip)(Hip)2]·4H2O has been synthesized by the reaction of Cu(CH3COO)2·H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: mono- clinic, space group C2/c, a = 19.214(3), b = 10.6973(14), c = 22.567(3) , β = 105.081(2)°, C24H19N2O8Cu, Mr = 526.95, Z = 8, F(000) = 2160, V = 4478.6(10) 3, Dc = 1.563 g/cm3, μ = 1.030 mm-1, –24≤h≤16, –13≤k≤13, –28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 (Rint = 1.0357) independent reflections and 3290 observed ones (I > 2σ(I)). Structural analysis shows that coordination geometry of Cu(Ⅱ) is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.     

Hydrothermal Syntheses and Structural Characterizations of Two ML-Containing Polyoxomolybdates:[Cu~Ⅱ_2(HL)_3]_2[Mo_8O_(26)]·(H_2O)_4 and [Ni~Ⅱ(HL)_3]_2(Mo_8O_(26))·(H_2O)_3(HL=3-(2-Pyridyl)pyrazole)

Two new polyoxomolybdate compounds,namely CuII2(HL)3]2[Mo8O26]·(H2O)4(1) and [NiII(HL)3]2(Mo8O26)·(H2O)3(2)(HL = 3-(2-pyridyl)pyrazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one β-Mo8O264-cluster and a Cu2 dimer which is built from two Cu(II) ions linked by three 3-(2-pyridyl)pyrazole ligands.Compound 2 is generated by two kinds of polyoxomolybdate clusters of α-[Mo8O26]4-and β-[Mo8O26]4-.In complexes 1 and 2,the multi-dimensional frameworks are con-structed with the help of hydrogen-bonding links between the terminaloxygen atoms of [Mo8O26]4-,water molecules,and 3-(2-pyridyl)pyrazole ligands.Crystal data of 1:C24H25Cu2Mo4N9O15,Mr = 1190.37,monoclinic,space group P21/c,a = 10.850(2),b = 18.510(4),c = 17.230(3) ,β = 100.57(3)°,V = 3401.6(12) 3,Z = 4,Dc = 2.324 g/cm3,F(000) = 2312,μ = 2.742 mm-1,R = 0.0302 and wR = 0.0775(Ⅰ 2σ(Ⅰ));Crystal data for 2:C48H48Mo8N18Ni2O29,Mr = 2225.98,monoclinic,space group P21/n,a = 20.799(2),b = 14.7970(13),c = 23.141(2) ,β = 91.6180(10)°,V = 7119.0(11) 3,Z = 4,Dc = 2.077 g/cm3,F(000) = 4344,μ = 1.968 mm-1,R = 0.0309 and wR = 0.0696(Ⅰ 2σ(Ⅰ)).     

Synthesis and Crystal Structure of a New Complex {[Co~(Ⅲ)L_2]·[Co~(Ⅱ)(H_2O)_6]_(0.5)·2.25H_2O}_4 (H_2L = N-(2-Hydroxyphenyl)salicylidenimine)

The reaction of Co(OAc)2·4H2O with the Schiff base H2L in a methanol solution affords the red crystals of {[CoIIIL2]·[CoII(H2O)6]0.5·2.25H2O}4 1 (H2L = N-(2-hydroxyphenyl) sali-cylidenimine). The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n, C104H114Co6N8O37, Mr = 2421.61, a = 10.625(3), b = 16.335(4), c = 15.265(4) , β = 102.990(4)o, V = 2581.6(11) 3, Z = 1, Dc = 1.558 g/cm3, μ = 1.034 mm-1, F(000) = 1252, R = 0.0414 and wR = 0.1167 for 5889 reflections. The Co(III) atom is six-coordinated by two nitrogen atoms and four oxygen atoms of two tridentate L ligands. The abundant hydrogen bonding interactions extend the complex into a one-dimensional supra-molecular framework. The uncoordinated water molecules act as space-fillers and consolidate the whole architecture through the hydrogen bonding interactions.     

A Novel Hybrid Solid Constructed from Tetramolybdate and Copper Complexes with Mixed Ligands: [{(Cu·phen)_2(tp)}{(Cu·phen·H_2O)_2(tp)}{Mo_4O_(14)}]

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.     

Synthesis,Structure and Characterization of [Cu(2,2′-bpy)_2][{Cu(2,2′-bpy)_2}_2W_(12)O_(40)(H_2)]·4H_2O

An organic-inorganic compound [Cu(2,2′-bpy)2][{Cu(2,2′-bpy)2}2W12O40(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O, 2,2′-bipyridine (2,2′-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9) , β = 96.992(3)°, V = 8365.0(6) 3, Dc = 3.214 g/cm3, Z = 4, μ(MoKα) = 17.269 mm-1 and F(000) = 7324. Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2′-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2′-bpy)2]2+ cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2′-bpy)2}2+ groups through bridging oxygen atoms.     

Synthesis and Crystal Structure of [Cu_2(DMF)(H_2O)(C_7H_4NO_4)_2(C_7H_3NO_4)]_2·3.5DMF

A new copper(II) complex [Cu2(DMF)(H2O)(C7H4NO4)2(C7H3NO4)]2·3.5DMF has been synthesized and its structure was determined by single-crystal X-ray diffraction.The crystal is of triclinic,space group P1 with a = 10.722(3),b = 18.170(4),c = 20.923(7),α = 105.297(9),β = 101.701(10),γ = 105.74(1)°,V = 3615(1) 3,Z = 2,C58.50H64.50Cu4N11.50O31.50,Mr = 1686.90,Dc = 1.550 g/cm3,μ = 1.255 mm-1,F(000) = 1728.00,T = 150(2) K,the final R = 0.0640 and wR = 0.173 for 11310 observed reflections with I > 2σ(I).In the crystal,each formular unit consists of two dinuclear copper(II) compounds,between which the O-H···O hydrogen bonds exist.Each CuII cation is six-coordinated in an octahedral geometry.The intermolecular hydrogen-bonding interaction leads to a 3-D framework of the title compound.     

Synthesis and Crystal Structure of [{Cd(hmbdc)(H_2O)_3}·2H_2O]_n

A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc = 5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a = 9.599(3), b = 18.699(5), c = 7.557(2) , β = 108.198(4)°, V = 1288.6(6) 3, Z = 4, Mr = 382.60, Dc = 1.972 g/cm3, F(000) = 760, μ = 1.740, the final R = 0.0555 and wR = 0.0995 for 1732 observed reflections with I > 2σ(I). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.     

Hydrothermal Synthesis of a 1D Paddle-wheel Cu(Ⅱ) Coordination Polymer {[Cu_2(NBDOA)_2·(H_2O)_2]·2(H_2O)}_n Constructed by Flexible Carboxylic Acid

A 1-D paddle-wheel copper (II) coordination polymer constructed by 2-nitro-benzene-1,4-di(oxyacetic) acid has been synthesized by hydrothermal reaction,and its crystal structure was determined by X-ray diffraction. The crystal is of triclinic,space group P1 with a=7.7257(12),b=8.3648(13),c=11.5516(18),α=76.654(2),β=82.088(2),γ=63.636(2)o,C20H22Cu2N2O20,Mr=737.48,V=650.27(18)3,Dc=1.883 g/cm3,F(000)=374,μ=1.737 cm-1 and Z=1. The final refinement gave R=0.0345 and wR=0.0995 for 1996 observed reflections with I > 2σ(I). The coordination polymer demonstrates a 1-D microporous structure,and the channel is formed by two NBDOA2-and two Cu2+ ions. The ligand NBDOAH2 displays a good flexible characteristic. The 1-D chains are connected to a 3-D supramolecular network by hydrogen bonds.     

Synthesis and Structural Characterization of a Polyoxomolybdate HNa_7[Mo_(36)O_(112)(H_2O)_(16)]·47H_2O

A new polyoxomolybdate complex HNa7[Mo36O112(H2O)16]·47H2O 1 has been prepared in the beaker solution and characterized by single-crystal X-ray diffraction and elemental analyses. Crystal data: H127Mo36Na7O175, Mr = 6542.79, monoclinic, C2/c, a = 40.891(6), b = 17.900(3), c = 25.580(4) , β = 125.673(2)°, V = 15210(4) 3, Z = 4, Dc = 2.857 g/cm3, F(000) = 12464, μ = 3.013 mm-1, R = 0.0633 and wR = 0.1654 (I > 2σ(I)). With the bridging sodium cations, the [Mo36O112(H2O)16]8- units in compound 1 are linked to form a one-dimensional structure, on the basis of which a three-dimensional architecture is further constructed via other sodium cations and complicated hydrogen bonds.     

Synthesis,Structure, and Luminescent Property of a 3-D Strontium Complex [Sr_3(pda)_2(Hpda)_2(H2O)_2]_n·2nH_2O

The title complex [Sr3(pda)2(Hpda)2(H2O)2]n·2nH2O(H2pda = pyridine-2,6-dicar- boxylic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 10.3795(8), b = 9.2225(7), c = 18.5726(14) , β = 104.377(2)o, V = 1722.2(2) 3, C28H22N4O20Sr3, Mr = 997.36, Z = 2, Dc = 1.923 g/cm3, μ = 4.722 mm-1, F(000) = 984, the final R = 0.0269 and wR = 0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.     

Mo_8~ⅤW_2~ⅥO_(26)(C_5H_5N)_8·2H_2O: A Novel Mixed-valence Heterometal Polyoxometalate

A new mixed-valence heterometal cluster Mo8VW2VIO26(C5H5N)8·2H2O has been synthesized under solvothermal conditions and characterized by X-ray single-crystal diffraction, IR, UV-vis and XPS spectroscopy. The title compound crystallizes in the triclinic system, space group P1 with a = 11.708(3), b = 12.018(4), c = 13.316(4) , a = 112.184(4), β = 97.844(4), r = 110.043(3)o, V = 1551.9(8) 3 and Z = 1 at 293(2) K. The final full-matrix least-squares refinement converged to R = 0.0414 for 4460 observed unique reflections with I 2σ(I) and w R = 0.1290 for all data(5352) and S = 1.015. In addition, its thermal stability and fluorescent property have also been investigated.     

Synthesis and Characterization of a Bismuth Incorporating Heptamolybdate:(NH_4)_4[HMo_7O_(24)Bi(H_2O)_2C_5H_3N(CO_2)_2]·7H_2O

A new one-dimensional molecule based on the linkage of [Mo7O24] clusters and [BiL](L = pyridine-2,6-dicarboxylic acid) assembles under ambient conditions. The title compound was characterized by X-ray powder diffraction, IR and UV spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. Crystal data: C7H38BiMo7N5O37, Mr = 1664.95, monoclinic, space group C2/c, a = 24.312(2), b = 21.4869(18), c = 18.5423(16) , β = 111.6490(10)o, V = 9002.9(13) 3, Z = 8, μ = 5.883 mm–1, F(000) = 6304, GOF = 1.045, R = 0.0365 and wR = 0.1062.     

Synthesis and Crystal Structure of a New Complex [Cu（C_（14）H_9O_3）_2（C_5H_5N）_2（C_2H_5OH）_2]

The title compound of Cu(C14H9O3)2(C5H5N)2(C2H5OH)2(1) was synthesized via the hy- drothermal reaction of CuCl2·2H2O and 9-hydroxy-fluorene-9-carboxylic acid(HHF) with pyridine, and characterized by elemental analysis and infrared spectra. The crystal belongs to triclinic, space group P1 with a = 8.8302(12), b = 10.1625(14), c = 12.2708(17), α = 86.207(2), β = 69.562(2), γ = 64.932(2)o, V = 930.3(2) 3, Z = 1, Mr = 764.30, Dc = 1.364 g/cm3, F(000) = 399, S = 1.059 and μ(MoKα) = 0.644 mm-1. The final R = 0.0459 and wR = 0.1274 for 3414 observed reflections with I 2σ(I). The copper atom is six-coordinated by two oxygen atoms from two different 9-hydroxy-fluorene-9-carboxylate ligands, two pyridine nitrogen atoms and two ethanol oxygen atoms, forming a distorted octahedral coordination geometry. The extensive O–H···O hydrogen bonding connects the molecules to form a one-dimensional chain structure. Between adjacent one-dimensional chains, a two-dimensional layered structure was formed by fluorene ring π-π packing interaction. Between the layers, a three-dimensional structure was formed through the π-π packing interaction of the pyridine ring. Moreover, the thermal stability and photoluminescent property of the complex has been investigated.     

Synthesis, Crystal Structure and Luminescence Property of [Co(hmz)_2(H_2O)_4]·2H_2O

A new mononuclear Co(II) complex, [Co(hmz)2(H2O)4]·2H2O, has been synthesized by the reaction of Co(CH3COO)2·4H2O with 1-(4-hydroxyphenyl)-5-mercaptotetrazole (Hhmz). It crystallizes in the monoclinic system, space group P21/n with a = 13.502(5), b = 6.718(3), c = 13.972(6) , β = 117.532(4)o, V = 1123.9(8) 3, Z = 2, M r = 553.45, F(000) = 570, Dc = 1.635 g/cm3, μ = 1.008 mm–1, the final R = 0.0272 and wR = 0.0684 for 2194 observed reflections (I > 2σ(I)). The Co(II) is six-coordinated by two nitrogen atoms from two hmz–1 ligands and four water molecules, forming an octahedral geometry. The intermolecular hydrogen bonding and offset-panel π-π stacking interactions between the adjacent molecules extend the compound into a three- dimensional supramolecular framework. The title compound emits strong blue fluorescent light (λem(max) = 427 nm) at room temperature and is red-shifted compared with free ligand Hhmz (λem(max) = 342 nm).     

Synthesis and Crystal Structure of a Copper(Ⅱ) Compound with 4-Hydroxybenzoic Acid and Isonicotinamide:[Cu(4-hba)_2(inta)(H_2O)]·H_2O

A new copper(Ⅱ) compound has been prepared and fully characterized by elemen-tal analysis,IR,TG and single-crystal X-ray diffraction.The compound [Cu(4-hba)2(inta)(H2O)]·H2O (4-hba=4-hydroxybenzoic acid,inta=isonicotinamide) 1 crystallizes in the monoclinic system,space group P21/c with a=7.590(5),b=11.027(5),c=23.761(5),β=102.5740(10)o,V=1974.1(16) 3,Mr=991.84,Z=2,Dc=1.669 g/cm3,F(000)=1020,μ=1.166 mm-1,R=0.0353 and wR=0.0604 for 3166 observed reflections (I 2σ(I)).In compound 1,the copper cation is penta-coordinated with two carboxylate oxygen atoms from two different 4-hba ligands,two oxygen atoms from two coordinated water molecules and one nitrogen atom from inta ligand,showing a slightly distorted square-pyramidal geometry.     

Synthesis,Crystal Structure and Characterization of a New Tetra-nuclear Lead Complex:[Pb_4(1,2-bdc)_4(L)_2]·2.25H_2O

The title complex,[Pb4(1,2-bdc)4(L)2]·2.25H2O 1(L = 2-(2-chloro-6-fluorophen-yl)-1H-imidazo[4,5-f][1,10]phenanthroline,1,2-H2bdc = 1,2-benzenedicarboxylic acid),has been obtained by using hydrothermal synthesis and characterized by elemental analysis,IR and single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a = 12.0920(6),b = 18.9248(10),c = 15.2729(8) ,β = 98.7530(10)°,V = 3454.3(3) 3,Z = 1,C140H90Cl4F4N16O41Pb8,Mr = 4527.60,Dc = 2.176 g/cm3,F(000) = 2130,μ(MoKa) = 9.884 mm-1,R = 0.0241 and wR = 0.0582.Compound 1 exhibits a unique tetra-nuclear structure,and is further stacked by π-π interactions to give a two-dimensional supramolecular layer.The N-H···O and O-H···O hydrogen bonds stabilize the structure of 1.     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6(phCH_2NC_5H_5)3]·(H_2O)_4

A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) , β = 97.531(4)o, V = 4161.0(15) A3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N+C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O–H···N and O–H···O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N+C5H5)3] ions are bound by electrostatic force to form an ionic compound.     

Synthesis,Structure,Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[Cd[μ-(4,4′-dps)]_2(H_2O)_2]·(4-abs)_2(H_2O)_2}_n

A new cadmium(II) compound, {[Cd[μ-(4,4'-dps)]2(H2O)2]·(4-abs)2(H2O)2}n 1 (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) , V = 3831.8(8) 3, 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.