Triply-bridged Dicopper(Ⅰ)Complex of Bis(diphenylphosphino)acetylene with a Helical Coordination Cage

<正>Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (I) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the CuACu separation of 6.231 A. The copper (I) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P 1 with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3) A, α = 98.289(1), β = 91.232(1), γ = 106.496(1)°, V = 4117.60(9) A3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr= 1659.37, Dc= 1.338 g/cm3, F(000) = 1708, μ = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I>2σ(I).     

Crystal Structure of Copper（ Ⅱ）Complex with 3—Hydroxyl—1,5—diazaylo

Crystal structure of copper (II) complex with a new aminocarboxylate ligand, 3-hydroxyl-1, 5-diazacycloheptane-N,N-diacetate, C9H14CuN2O5.H2O, Mr=311.78 is reported. It crystallizes in orthorhombic Pna21 with a=13.340(4), b=8.127(1), c=10.583(4) , V=1147.2(7)3 , Z=4, Dc=1.805g/cm3, μ=19.287cm-1 (MoKα), F(000)=644. The final R and Rw are 0.049 and 0.065 for 888 observed reflections with I≥3σ(I). The result of X-ray structure determination shows that the Cu(Ⅱ) forms a planar complex with two oxygen atoms and two nitrogen atoms of the ligand.     

Crystal Structure of Copper(II) Complex with 3-Hydroxyl-1,5-diazacycloheptane-N,N-diacetate

Crystal structure of copper (II) complex with a new aminocarboxylate ligand, 3-hydroxyl-1, 5-diazacycloheptane-N,N-diacetate, C9H14CuN2O5.H2O, Mr=311.78 is reported. It crystallizes in orthorhombic Pna21 with a=13.340(4), b=8.127(1), c=10.583(4) , V=1147.2(7)3 , Z=4, Dc=1.805g/cm3, μ=19.287cm-1 (MoKα), F(000)=644. The final R and Rw are 0.049 and 0.065 for 888 observed reflections with I≥3σ(I). The result of X-ray structure determination shows that the Cu(Ⅱ) forms a planar complex with two oxygen atoms and two nitrogen atoms of the ligand.     

Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ)Complex with 4,4',6,6'-Tetrabromo-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol

A new mononuclear Cu(Ⅱ)complex,[Cu(L)](H2L=4,4',6,6'tetrabromo-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol),has been synthesized and structurally characteri-zed.X-ray crystal stucture of the complex reveals that the Cu(Ⅱ)ion is four-coordinated by two oxygen atoms and two nitrogen atoms from L2-unit.Crystallographic data:monoclinic,space group P21/n with a=14.076(2),b=6.9801(14),c=19.858(2)(A),β=107.613(2)°,C16H10Br4CuN2O4,Mr =677.44,V=1859.6(5)(A)3,Dc=2.420 g/cm3,μ=9.796 mm-1,F(000)=1284,Z=4,the final R=0.0516 and wR=0.0938 for 1879 observed reflections with I＞20(I).The dihedral angel between the two coordination planes of Cu(1)-N(2)-O(4)and Cu(1)-N(1)-O(3))is 30.08(6)°.     

Synthesis and Crystal Structure of the Copper(Ⅱ) Complex with Tris- (1,10-phenanthroline-5,6-dione)

The title complex [ CuL3 ] (C1O4)2 · 2H2O· 2CH3CN (L = 1, 10-phenanthroline-5, 6-dione) has been synthesized and characterized by elemental analysis, conductivity, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex (C40H28Cl2 CuNsO16, Mr = 1011.14) crystallizes in orthorhombic system, space group P21 21 21 with a = 13. 983(1), b = 14. 310 (1), c =20.890(2) (A。), V = 4179.7(6) (A。)3, Z = 4, Dc= 1.607g/cm3, F(000) = 2026,μ(MoKa) = 0.736 mm-1. The final R and w,R factors are 0.0446 and 0. 1212 respectively with 8545 independent reflections. The title complex is composed of a discrete [CuL3 ]2+ cation, uncoordinated ClO4- anions, H2O and CH3CN molecules. The central Cu(Ⅱ) atom is six-coordinated by six nitrogen donors of three ligands. The coordination geometry of Cu(Ⅱ) could be considered as an approximately ideal octahedral configuration with little static Jahn-Teller distortion (the longest and shortest Cu- N bonds are 2. 102 vs 2. 139 (A。) with the mean length of 2. 122 (A。) ), which is very rare for a six-coordinated Cu(Ⅱ) complex.     

1-D Open-channeled 3-D Supramolecular Frameworks Built with 2,3-Dihydroxybutanedioic Acid (H4dhbd) and 2,2':6,2"-Terpyridine (tpy)

The complex [Cu2(H2dhbd)2(tpy)2]·CH3OH·4H2O1 (H4dhbd=2,3-dihydroxybutane-dioic acid, tpy=2,2":6',2"-terpyddine) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups P1 with a=8.6859(17), b=11.223(2), c=12.275(2)A,α=112.454(3), β=98.435(3),γ=105.593(3)°, V=1022.5(3) A3, Z=1, C38H42Cu2N6.O18, Mr=997.86, Dc=1.621 g/cm3,μ=1.127 mm-1, F(000)=514, T=293(2) K, the final R=0.0539 and wR=0.1394 for 3550 observed reflections with 1 >20(1). In the dinuclear unit, two CuⅡ atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526(12)A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between CuⅡ ions.     

Synthesis and Crystal Sturcture of a New Praseodymium（Ⅲ）polym煳x：[

A novel polymeric Pr2Cu3 complex of iminodiacetic acid (H2L1=NH{CH2COOH}2) [Pr2Cu3(L1)6]n , 1, has been synthesized and structurally characterized. The title complex Pr2Cu3O24N6C24H30 (Mr=1258.97) crystallized in trigonal space group Pc1 (No. 165) with a = 13.424(4), c=14.752(6)(); V=2303(1)()3; F(000)=1226; λ(MoKα)=35.2 cm-1; Dc=1.820 g.cm-3; Z=2. The final R and Rw are 0.072 and 0.081 respectively for 1412 reflections with I>3σ(I). In crystal 1, the Pr3+ ion is nine-coordinated by 6 O atoms from three bidentate chelating carboxylate groups and 3 O atoms from three anti-anti bridging carboxylic groups of six L1 ligands; the Cu2+ ion is six-coordinated by 4 O and 2 N atoms from two pentadentate L1 ligands. Each pair of Pr(Ⅲ) atoms is bridged by three L1 ligands, each of which also chelates with one copper(Ⅱ) ion, thus forming a Pr2Cu3 cluster unit. Such cluster units are cross-linked by flexible L1 ligands into a three-dimensional coordination framework.     

Structure of Palladium( Ⅱ ) Complex with 2-Hydroxy-propane 1, 3-diamine-N,N,N'''' N'''',-tetraacetic Acid

The reaction of PdCl2 in water with 2-hydroxypropane-1, 3-diaminetetraacetic acid (HPDTA) gave the complex Pd (C11H16N2O9)·1. 5H2O, which was characterized by elemental analysis, IR, NMR and single-crystal X-ray diffraction. The spectroscopic and X-ray diffraction data show that Pd ( Ⅱ ) is coordinated by two nitrogen atoms and two car-boxylic oxygen atoms. The complex crystallizes in monoclinic space group Pc with a = 1. 1240(2), b=1. 1183(2), c=1. 2597(3) nm, β=96. 33(2)°V=1. 5737(6) nm3, Z = 4, R= 0.038. The structure contains two crystallographically independent molecules which have slightly different orientations and are connected by hydrogen bonds.     

Synthesis and Crystal Structure of Complex {[Cu(N-men)_2(cda)_2]·[Cu(N-men)_2]·(ClO_4)_2}(N-men=N-Methylethylenediamine,cda=Carbamyldicyanomethanide Anion)

<正>Mononuclear complex {[Cu(N-men)2(cda)2]·[Cu(N-men)2]-(ClO4)2} was synthesized by sodium carbamyldicyanomethanide Na(cda), N-methylethylenediamine and hydrate copper perchlorate. The crystal belongs to the triclinic system, space group P 1 with a = 7.229(2), b = 8.114(2), c = 15.936(4) A, α = 80.511(4), β = 78.993(4), r= 72.118(4)°, V = 867.6(3) A3, Z = 1, C20H44Cl2Cu2N14O10, Mr = 838.68, Dc = 1.605 g/cm3, F(000) = 434 and μ = 1.449 mm-1. The structure was refined to R = 0.0480 and wR = 0.1289 for 2503 observed reflections (I > 2σ(I)). In the complex there exist two kinds of coordination models for Cu (II) ions. One is that the Cu (II) ion is coordinated by four nitrogen atoms which are from two N-men molecules, and a slightly distorted square planar coordinate environment is formed around the Cu (II) ion; the other is that the Cu (II) ion is coordinated by six nitrogen atoms, of which four are from two N-men molecules and the left from nitrile groups, resulting in a distorted octahedron around the     

Synthesis and Characterization of a Novel 3D Coordination Polymer Based on Cu(Ⅱ) Cations and Mellitic Acid

A new mellitate complex [Cu3(μ2-mellitate)(μ2-H2O)(H2O)2·H2O]n 1 has been synthesi- zed by the reaction of mellitic acid and Cu(CH3COO)2·H2O in the presence of base. Crystallogra- phic data for 1: C12H80O16Cu3, Mr = 598.80, orthorhombic, Pbcn, a = 8.4378(6), b = 10.0396(7), c = 17.6799(12) A, V = 1497.70(18) A3, Z = 4, Dc = 2.656 g/cm3,μ = 4.327 mm-1, F(000) = 1180, R = 0.0431 and wR = 0.0964 for 1075 observed reflections (Ⅰ> 2σ(Ⅰ)). X-ray crystal structural analysis revealed that the mellitate anions behave as the bridging ligands and link eight copper atoms repeatedly to form a novel three-dimensional metal-organic coordination polymer with two different rhombic tunnels in the solid-state structure.     

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.     

Structure and Luminescence Property of a Linear Tetranuclear Gold(Ⅰ)-thiolate Complex through Au-Au Interaction

The synthesis,structure and luminescent property of a tetranuclear gold(Ⅰ)complex with doubly bridging diethyldithiocarbamate(Et2dtc)and 1,1-bis(diphenylphosphino)ethene((Ph2P)2C=CH2)are described.The complex crystallizes in monoclinic space group C2/c with a=26.785(7),b=25.654(6),c=12.277(3)A,β=106.879(5)°,V=8073(4)A~3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm~3,F(000)=4592,Rint=0.0529,T=293(2)K,μ=8.157 mm~(-1),the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I2σ(Ⅰ).The intramolecular and intermolecular Au¨Au distances are 2.8670(9)and 3.2367(9)A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.     

Synthesis and Crystal Structure of 3,3''-Bis(2-benzimidazolyl)-2,2''-dipyridine with Hydrated Zinc(Ⅱ) Perchlorate

The reaction of Zn(ClO4)2·6H2O with 3,3'-bis(2-benzimidazolyl)-2,2'-dipyridine (L) gave a mononuclear zinc(Ⅱ) complex: [ZnL2](ClO4)2·2DMF·4H2O, which was structurally characterized by EA, IR, UV, 1H NMR, fluorescence spectrum and single-crystal X-ray diffraction. The crystal (C54H54Cl2N14O14Zn, Mr=1259.38) belongs to the monoclinic system, space group C2/c with a=20.874(2), b=14.9953(16), c=20.462(3) (A), β=101.553(2)°, V=6274.8(13) (A)3, Z=4, Dc=1.333 g/cm3, F (000)=2608, μ(MoKα)=0.548 mm-1, R=0.0682 and Wr=0.1931 for 4984 observed reflections with Ⅰ ＞ 2σ(Ⅰ). The Zn(Ⅱ) is four-coordinated in a slightly distorted tetrahedral geometry through four N atoms from four benzimidazole units of two ligands. In the crystal lattice, the [ZnL2]2 cations are linked to each other by extensive intermolecular hydrogen bonds between nitrogen atoms of benzimidazole rings, water and DMF molecules.     

Synthesis and Crystal Structure of a 2D Cu Framework Constructed from Dinuclear Building Units

A novel 2D Cu coordination polymer [Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O]n(2, H2 pca = pyrazole-3-carboxylic acid) has been prepared by dissolving a dinuclear Cu complex Cu2(py)3(pca)2(H2O)·(H2O)(1) in DMSO solution and structurally characterized by X-ray diffraction. The polymer crystallizes in space group P1 with a = 9.538(3), b = 9.714(3), c = 10.765(3) A, α = 86.492(6), β = 84.007(7), γ = 82.592(6)o, Mr = 1079.04, V = 982.4(5) A3, Z = 1, Dc = 1.824 g/cm3, μ = 2.425 mm-1 and F(000) = 548. The final refinement gave R = 0.0785 and w R = 0.1940 for 2787 reflections with I 2σ(I). The structure of 2 consists of Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O units, which can be viewed as two dinuclear subunits of Cu2(pca)2(H2O)2 and Cu2(pca)2(DMSO)2 connected to each other alternately, with solvent DMSO and H2 O molecules around. The framework features a grid-like topology, with the walls of the grids composed of Cu4(pca)4 units, and the coordinated solvent molecules trapped in the grids.     

Synthesis and Crystal Structure of a Cu2+ Supra-molecular Complex [Na2Cu(BTA)2(H2O)8]·H2Owith a Three-dimensional Network Structure

A three-dimensional Cu2+ supramolecular complex [Na2Cu(BTA)2(H2O)8]·H2O 1 (H2BTA = bistetrazolylamine) was synthesized by reacting the aqueous solution of CuSO4·5H2O and H2BTA under stirring. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The result indicates that 1 crystallizes in triclinic,space group P1,with a = 7.0518(2),b = 12.2692(2),c = 13.8583(3) ,α = 115.7260(10),β = 93.2440(10),γ = 98.3610(10)o,Mr = 573.90,V = 1059.01(4) 3,Z = 2,Dc = 1.800 g·cm-3,μ(MoKα) = 1.155 mm-1,F(000) = 586.0,S = 1.074,the final R = 0.0273 and wR = 0.0744 for 4334 observed reflections with Ⅰ > 2σ(Ⅰ). The Cu2+ ion is five-coordinated with a N4O1 donor set with τ = 0.153 according to the method of Addison et al. And the Na+ ions form an infinite main chain through bridging O atoms from coordinated water molecules. In 1,a three-dimensional supramolecular network is formed by O-H···O,O-H···N,N-H···O and N-H···N hydrogen bonds.     

Synthesis and Crystal Structure of Bis{2-bromo- 4-chloro-6-[（2-isopropylammonioethylimino）- methyl]phenolato}bisthiocyanatozinc（Ⅱ）

A Schiff base zinc(Ⅱ) complex [Zn(C12H16BrClN2O)2(NCS)2] was prepared and characterized by elemental analysis,IR and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1 with a=8.414(1),b=9.124(1),c=22.212(3),α=79.177(2),β=86.296(2),γ=89.899(2)o,V=1671.3(4)3,Z=2,Dc=1.631 g/cm3,Mr=820.79,λ(MoKα)= 0.71073,μ=3.444 mm-1,F(000)=824,R=0.0646 and wR=0.1179. A total of 7371 unique reflections were collected,of which 3904 with I > 2σ(I) were observed. The complex crystallizes with two half-molecules per asymmetric unit and each mononuclear molecule is centrosymmetric. The Zn atom lying at the inversion centre is six-coordinated in a slightly distorted octahedral geometry by two phenolate O atoms and two imine N atoms from two Schiff base ligands,as well as two N atoms from two thiocyanate anions. In the crystal structure,the combination of π-π stacking interactions and intermolecular hydrogen bonds (N–H…Br,N–H…O,N–H…N,C–H…O,C–H…S and C–H…Cl) leads to a three-dimensional network.     

杂-双核配合物[CaCu(C3H2O4)2(H2O)4]n的合成、晶体结构及热稳定性

The title complex, [CaCu(C3H2O4)2(H2O)4]n, with a formula of C6H12CaCuO12 and Mr=379.78 has been sy-nthesized and characterized by single crystal X-ray diffraction structure analysis, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is Orthorhombic, space group Pbcn with a=0.669 21(5) nm, b=1.370 23(5) nm, c=1.322 39(10) nm, V=1.212 59(16) nm3, Dc=2.080 g·cm-3, μ=2.288 mm-1, F(000)=772 and Z=4. The final R=0.054 0 and wR=0.112 8 for 1 189 observed reflections with I>2σ(I). The structure of the title complex consists of CaO8 polyhedra and CuO6 elongated octahedra linked together by malonate ligands. The Ca(Ⅱ) cation, on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Cu(Ⅱ) cation, which lies in a centre of symmetry in an octahedral arrangement, is coordinated by four malonate O atoms and two water molecules. The structure comprises alternating layers along the [101] plane, with the shortest Cu…Cu distance of 0.762 46(6) nm. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds. Its thermo gravimetric analysis was determined by TG-DTG techniques. CCDC:663184.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A MOLYBDENUM-COPPER-SULFUR CLUSTER COMPLEX WITH DITHIOBENZOATE LIGAND [Bu_4N]_2[MoCu_2S_4(C_6H_5CS_2)_2]

<正> The title compound has been synthesized by the reaction of (Bu4N)2MoS4, CuCl and (C6H5CS2)(Bu4N) in DMF and recrystallized from DMF/ Et2O. The red black crystal belongs to the triclinic space group P1 with a = 12. 021 (6), b = 17.045(8), c=17. 136(7)(?) , α=110.05(3), β=108.64(4), γ=103.87 (4)°, V = 2873(3)(?)3, Dc=1. 321gcm-3, Z = 2. The structure was refined to R = 0. 065 for .4783 reflections. The anion of the title compound can be described as a MoS42- tetrahedron coordinated by two [Cu(C6H5CS2)] units with the three metal atoms lying on a line. The coordination number of each Cu atom is three.     

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C13H9N2O)Cl]2·(CH3CN)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 triclinic system, space group P1-, with a = 7.6677(14), b = 9.2375(17), c = 11.227(2) (A), α = 81.338(3),β= 88.173(4), γ = 66.199(3)°, V = 718.9(2) (A)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) (A).     

Crystal Structure and Properties of a Copper(Ⅱ) Complex Containing p-Toluenesulfonate and Imidazole Ligands

A novel supramolecular mixed ligand complex of formula [Cu(PTS)2(Him)2(H2O)2] (C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole) has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650(2),b=14.671(3),c=14.638(3),β=100.10(3)°,V=1194.60(4)3,Dc=1.607 g/cm3,μ(MoKα)=1.143 mm-1,F(000)=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 2σ(I).The copper(II) ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.