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.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy

Two new cobalt（II） supramolecular complexes [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O 1 and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy 2 based upon the assembly of Co（II）, 4,4＇-bipyridine （4,4＇-bipy） and two new multifunctional organic ligands, 2,4,6-tris（4-sulfophenyl- amino）-1,3,5-triazine （H3TST） and 2,4-bis（p-sulfanilato）-6-diethylamino-1,3,5-triazine （H2DSNT）, have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P21/n with a = 13.599（4）, b = 18.988（6）, c = 22.995（7） A, β = 90.273（6）°, V = 5938（3）A^3, Z = 4, C56H59Co1.5N13O17S3, Mr = 1370.74, Dc = 1.533 g/cm^3, μ = 0.613 mm^-1, F（000） = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I 〉 2σ（I）. The crystal structure of 2 belongs to the monoclinic system, space group C2/c with a = 18.864（6）, b = 14.283（5）, c = 20.246（7）A, β = 107.799（6）°, V = 5194（3）A^3, Z = 4, C49H52CoN12O10S2, Mr = 1092.08, Dc = 1.397 g/cm^3, μ = 0.480 mm^-1, F（000） = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I 〉 2σ（I）. The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

Synthesis,Structure,and Magnetic Property of One Snake-shaped Copper（Ⅱ）-organic Compound：Cu[Cu_2（PP）_2]（CBPC）_2]·2（H_2O）

One novel copper(II)-organic compound,namely Cu[Cu2(PP)2](CBPC)2]·2(H2O)(1,H2CBPC = 1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-(2-pyridyl)pyrazole),was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu(II)ions in the quasi-planar dimmer of [Cu2(PP)2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1:C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900(7),b = 15.029(7),c = 12.308(6),β = 102.519(9)o,V = 2691(2)3,Z = 2,Dc = 1.530 g/cm3,F(000)= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780(I > 2σ(I))and S = 0.999.     

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper（Ⅱ） Complex：[Cu_6（DPPZ）_4（btc）_4（H_2O）_8]·5H_2O

A new hexanuclear copper(Ⅱ) complex,[Cu 6 (DPPZ) 4 (btc) 4 (H 2 O) 8 ]·5H 2 O (1,DPPZ=dipyrido[3,2-a:2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid),has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489(4),b=14.234(5),c=14.484(5),α=82.848(4),β=79.399(4),γ=73.646(4)°,V=2421.2(13) 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F(000)=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I > 2σ(Ⅰ).In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.     

Synthesis, Crystal Structure and Thermal Stability of the Coordination Polymer [Co（2-mpac）_2（py）·4H_2O）]_n

A new coordination polymer with the formula of [Co(2-mpac)2(py)·4H2O)]n (1, 2-mpac = 5-methyl-2-pyrazinecarboxylic acid, py = pyrazine) has been synthesized through hydrothermal synthesis and structurally characterized by X-ray single-crystal diffraction method. 1 exhibits a 3D supramolecular network. Crystal data: monoclinic, space group C2/m, a = 15.907(9), b = 7.104(3), c = 9.793(5), β = 95.232(8)o, V = 1102.0(10)3, Z = 2, S = 0.995, the final R = 0.0509, wR = 0.1626 for 1002 observed reflections with (I > 2σ(I)) and R = 0.0530, wR = 0.1667 for all data. In addition, elemental analysis, IR and thermalgravimetric analysis are presented.     

Synthesis, Crystal Structure and Luminescent Properties of [Zn（bipy）_2（H_2O）_4]·L·3H_2O

A novel coordination complex [Zn(bipy)2(H2O)4]·L·3H2O (1, bipy = 4,4'-bipyridine, LHNa = aniline-2,5-disulfonic acid monosodium salt) has been synthesized from LHNa by using hydrothermal method and structurally characterized. The result indicates that complex 1 belongs to the monoclinic system, space group P21/c with a = 20.392(3), b = 7.4052(12), c = 23.843(3) , β = 116.253(10)°, V = 3.2291(8) 3, Z = 4, Dc = 1.553 g·cm-3, μ = 0.962 mm-1, F(000) = 1568, and the final R = 0.0497 and wR = 0.1290. The complex 1 has a 0-D discrete structure, and generates an infinite 3-D network with the aid of O–H…O hydrogen bonds and π-π interactions.     

Synthesis, Crystal Structure and Luminescent Property of a One-dimensional Zinc（Ⅱ） Complex

A metal-organic coordination polymer [Zn2(cbba)4(bix)2]n·nH2O (Hcbba = 2-(4′- chlorine-benzoyl)-benzoic acid, bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Pale yellow crystals crystallize in the triclinic system, space group Pī, a = 10.2796(13), b = 17.636(2), c = 23.237(3), α = 105.046(2), β = 102.534(2), γ = 100.758(2)o, V = 3837.0(9)3, C84H59Cl4N8O13Zn2, Mr = 1660.93, Dc = 1.438 g/cm3, F(000) = 1702, Z = 2, μ(MoKα) = 0.835 mm-1, the final R = 0.0525 and wR = 0.1211 for 9129 observed reflections (I > 2σ(I)). The structure of 1 exhibits a one-dimensional chain-like structure and shows yellow luminescent property at room temperature.     

Synthesis,Crystal Structure,Magnetic Property and DFT Study of a Novel 2D Polymer [Cu(pdc)(bpy)]·H_2O

A new copper complex [Cu(pdc)(bpy)]·H2 O(1, H2 pdc = 3,5-pyridinedicarboxylic acid, bpy = 2,2-bipyridine) has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectroscopy and magnetic measure- ments. Complex 1 crystallizes in monoclinic system, space group P21 /c, a = 10.893(2), b = 7.3641(15), c = 1.9921(4), β = 92.16(3), V = 1596.9(6)3, Dc = 1.676 g/cm3, Mr = 402.84, Z = 4, F(000) = 820, μ = 1.404 mm-1, the final R = 0.0237 and wR = 0.0693. The Cu(II) ion is five-coordinated by two O atoms from two pdc ligands, one N atom from another pdc ligand and two N atoms from the bpy ligand. The pdc anion, which acts as a tridentate ligand, links three Cu ions, forming(3,3)-connected two-dimensional(2D) sheets. We also studied the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with UV-vis spectrum.     

Hydrothermal Synthesis and Crystal Structure of a One-dimensional Copper（Ⅱ） Complex

A metal-organic coordination polymer [Cu(cbba)2(bix)]n(Hcbba = 2-(4'-chlorine-benzoyl)-benzoic acid,bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis,IR,TG,UV and single-crystal X-ray diffraction.Blue crystals crystallize in the monoclinic system,space group C2/c with a = 26.127(3),b = 10.6143(14),c = 14.5676(19) ,β = 111.289(2),V = 3764.3(8) 3,C42H30Cl2CuN4O6,Mr = 821.14,Dc = 1.449 g/cm3,F(000) = 1684,Z = 4,μ(MoKα) = 0.777 mm 1,the final R = 0.0528 and wR = 0.1200 for 2241 observed reflections(I > 2(I)).The structure of 1 exhibits a one-dimensional chain-like structure.     

Synthesis and Crystal Structure of a New Dimolybdenum（V） Complex Na4[Mo2O4（HNTA）2]2·19H2O

The new binuclear molybdenum（V） complex Na4[Mo2O4（HNTA）2]2·19H2O （NTA = nitrilotriacetate） has been prepared and characterized by single-crystal X-ray diffraction analysis and IR. The crystal has space group Pnma with a = 10.2239（2）,b = 23.8174（3）,c = 23.1845（4） A,V = 5645.58（16）A^3,Z = 4,C24H66Mo4N4Na4O51,Mr = 1702.50,Dc = 1.958 g/cm^3,μ = 1.027 mm^-1,F（000） = 3280,T = 293（2） K,the final R = 0.0609 and wR = 0.1449 for 5512 observed reflections （I 〉 2σ（I））. Each MoV atom has a distorted octahedral coordination geometry,and the two coordination octahedra share a common edge to form a dioxo-bridged Mo2O4 unit which is coordinated by NTA ligands. The dianionic binuclear units [Mo2O4（HNTA）2]^2- are interconnected by Na^＋ into a layered structure.     

Synthesis and Crystal Structure of a New Tetracopper Complex [Cu(H_2O)_3Cu(HCDTA)]_2(ClO_4)_2·H_2O

A new tetracopper complex [Cu(H2O)3Cu(HCDTA)]2(ClO4)2·H2O (CDTA = transcyclohexane-1,2-diamine-N,N,N′,N′-tetraacetate) has been prepared and characterized by singlecrystal X-ray diffraction analysis. The crystal adopts space group C2/c with a = 16.990(10), b = 9.150(5), c = 29.318(17) , β = 104.289(9)°, V = 4417(4) 3, Z = 4, C28H52Cl2Cu4N4O31, Mr = 1265.80, Dc = 1.904 g/cm3, μ = 2.130 mm-1, F(000) = 2584, T = 293(2) K, the final R = 0.0328 and wR = 0.0809 for 4938 observed reflections (I 2σ(I)). The tetracopper units are interconnected by weak covalent bonds into a layered structure.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Novel Water Cluster [Mn(phen)_2·H_2O·Cl]·p-FBA·3H_2O

A novel water cluster [Mn(phen)2·H2O·Cl]·p-FBA·3H2O (p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768(1),b = 11.5960(1),c = 12.9916(2) ,α = 101.816(2),β = 95.397(2),γ = 103.052(2)o,V = 1502.8(3) 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese(Ⅱ ) ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a (H2O)4 water cluster. This water pattern forms a cross-linked discrete ring. The steady (H2O)4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional (1D) structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Cobalt（Ⅱ） Complex with 2-Pyridinecarboxyic Acid and 4,4＇-Bipyridine Ligands

A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.     

Synthesis and Crystal Structure of a New Iron Complex with Cyclic Water Hexamers [Fe(CDTA)(H_2O)]·[Fe(1,10-phen)_3]·10H_2O·2OH

The title complex [Fe(CDTA)(H2O)]·[Fe(1,10-phen)3]·10H2O·2OH (CDTA = transcyclohexane-1,2-diamine-N,N,N,N′-tetraacetate) has been prepared and characterized by single-crystal X-ray diffraction analysis. The crystal adopts space group P with a = 12.793(4), b = 14.104(5), c = 17.880(5), V = 2792.2(1)3, Dc = 1.459 g/cm3, C50H66Fe2N8O21, Mr = 1226.81, F(000) = 1284, μ = 0.604 mm-1, Z = 2, R = 0.1055 and wR = 0.2581 for 8675 observed reflections (I > 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of two crystallographically independent molecules [Fe(CDTA)(H2O)] and [Fe(1,10-phen)3], and they are connected through O-H···O hydrogen bonds and π···π stacking interactions forming a 3D supramolecular structure. Interestingly, there is a cyclic water hexamer with chair conformation in this complex.     

Hydrothermal Synthesis,Structure and Magnetic Property of a Novel Hexa-Ni~Ⅱ Substituted Polyoxometalate

A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6（μ3- OH）3（en）3（H2O）6}（B-α-PW9O34）]-6H2O 1 （en = ethylenediamine） has been hydrothermally synthesized and characterized by IR spectra, elemental analysis, thermogravimetric analysis （TGA）, single-crystal X-ray diffraction and magnetic property. Compound 1 crystallizes in the hexagonal space R3c with a = 20.4124（5）, c = 21.4427（4）A, γ = 120.000°, V = 7737.5（3）A3, Z = 6, GOF = 1.083, R （wR） = 0.0317 （0.0610）. Single-crystal X-ray diffraction indicates that 1 contains a hexa-Nin substituted trivacant Keggin [{Ni6（μ3-OH）3（en）3（H2O）6}（B-α-PW9O34）] unit. The magnetic study shows the presence of ferromagnetic coupling interactions within hexa-Nin clusters with J1 = 0.69 cm-1 and J2 = 0.92 cm^-1 for 1.     

Synthesis,Crystal Structure and Magnetic Property of a New Cd（Ⅱ） Complex with Four Nitronyl Nitroxide Radicals

A new Cd(Ⅱ) complex with four nitronyl nitroxide radicals [Cd(NIT4Py)4Cl2](NIT4Py = 2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in triclinic,space group P1 with a = 7.2441(4),b = 13.6964(8),c = 13.7354(8) ,α = 89.8610(10),β = 77.9180(10),γ = 87.2250(10)°,V = 1331.01(13) 3,C48H64CdCl2N12O8,Mr = 1120.41,Z = 1,Dc = 1.398 g/cm3,μ(MoKα) = 0.573 mm-1,F(000) = 582,S = 1.043,the final R = 0.0257 and wR = 0.0641 for 4333 observed reflections(I > 2σ(I)).The title complex exists in the mononuclear-metal structures,in which each Cd(Ⅱ) ion adopts a distorted octahedral geometry and is coordinated by two Cl-anions and four pyridyl-N atoms from four NIT4Py ligands.The magnetic measurements show weak antiferromagnetic interactions between the nitroxide radicals.     

Hydrothermal Synthesis and Crystal Structure of a Three-dimensional Cadmium（II） Complex

A metal-organic coordination polymer [Cd2(PDC)2(bix)(H2O)2]n ·nH2O(H2PDC=2,4-pyridinedicarboxylic acid, bix=1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Brown crystals crystallize in the orthorhombic system, space group P2 12 12 1 with a=11.741(3), b=14.190(4), c=18.963(5) , V=3159.4(14) 3 , C28H26Cd2N6O11, Mr=847.35, Dc=1.781 g/cm3 , F(000)=1680, Z=4, μ(MoKα)=1.415 mm 1 , the final R=0.0381 and wR=0.0882 for 5472 observed reflections (I >2σ(I)). The structure of 1 exhibits a threedimensional network structure.     

Synthesis, Crystal Structure and Magnetic Properties of a Cobalt（II） Coordination Polymer with 4,4＇-（Propane-2,2-diyl）dibenzoate and 4,4 ＇-Bis（1-imidazolyl）biphenyl

A novel coordination polymer, {[Co（CBA）（BIMB）0.5]＇H20}n （1, H2CBA = 4,4＇- （propane-2,2-diyl）dibenzoic acid, and BIMB = 4,4＇-bis（1-imidazolyl）biphenyl）, has been hydro- thermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P2/c with a = 14.909（3）, b = 7.1963（15）, c = 24.592（5） A, β = 104.312（2）, V = 2556.5（9） A3, C26H23N2OsCo, Mr = 502.39, Dc = 1.305 g/cm3, F（000） = 1040,μ = 0.708 mm-1 and Z = 4. The final R= 0.0580 and wR = 0.1605 for 3228 observed reflections （1 〉 2a（I））. Single-crystal structure analysis shows that complex 1 exhibits a three-dimensional 2-fold interpenetrating pillared helical-layer open framework of a-Po topology based upon binuclear paddlewheel units. Moreover, its magnetic properties have also been investigated.     

Synthesis and Crystal Structure of One New Coordination Polymer： [Ni（qptc）0.5（bpp）（ H2O）]n

Solvothermal reaction of aromatic terphenyl-2,5,2?,5?-tetracarboxylic acid (H4qptc) ligand and the transitional metal cation of NiII in the presence of 1,3-bi(4-pyri- dyl)propane (bpp) affords one new coordination polymer, [Ni(qptc)0.5(bpp)(H2O)]n (1). The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, TGA, and magnetism. The qptc4- acts as a H-shaped ligand linking the NiII centers together to form a 2D polymeric [Ni(qptc)0.5]n layer consisting of alternately arranged left- and right-handed helical chains. Each 2D polymeric [Ni(qptc)0.5]n layer is further linked through the bridging bpp ligands, thus resulting in a unique (3,4)- connected network with the (62.8)(62. 84) topology. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 16.088(5), b = 14.913(5), c = 18.849(6) ?, β = 100.982(4), V = 4439(2) ?3, Z = 8, C24H21N2NiO5, Mr = 476.14, Dc = 1.425 g/cm3, F(000) = 1976 and μ(MoKα) = 0.912 mm-1. The final R = 0.0584 and wR = 0.1131 for 3894 observed reflections with I > 2σ(I) and R = 0.1224 and wR = 0.1279 for all data.