Syntheses,Crystal Structures and Properties of Co（Ⅱ） and Cu（Ⅱ） Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co(O2N-Hbtb)(phen)(H2O)3]·2H2O}n 1 and {[Cu3(O2N-btb)2(bipy)2(H2O)4]·4H2O}n 2(O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2'-bipyridine),were prepared through hydrothermal reactions of Co(Ⅱ) or Cu(Ⅱ) salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.     

Spectroscopic Studies of a Three-dimensional,Five-coordinated Copper(Ⅱ） Complex via Hydrogen Bonds:[Cu(PPD)(H2O)2](H2PDA=Pyridine-2,6-dicarboxylic Acid)

A new copper(Ⅱ） complex[Cu(PDA)(H2O)2] was synthesized and its structure was determined.Cu(Ⅱ）is five-coordinated in a tetragonal pyramid geometry.The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02nm.The whole crystal is linked to form a three-dimensional network by means of hydrogen bonds.The X-band ESR spectrum shows three different g tensors with a well-resolved hyperfine structure in the gz signal,giving the ESR parameters gx=2.05,gy=2.065 and gz=2.29.The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.     

Preparation,Structure, Fluorescence,Semiconductor Properties and TDDFT Calculation of a Mononuclear Zinc Complex with Mixed Ligands

A novel zinc complex[ZnL(bipy)(H2O)]×H2O with mixed ligands of 3-hydroxy-2-methylquinoline-4-carboxylic acid(HL)and bipy(bipy=2,2'-bipyridine)was synthesized by solvothermal reaction and its crystal structure was determined by single-crystal X-ray diffraction technique.The title compound crystallizes in the orthorhombic system of Pbca space group,and exists as an isolated mononuclear complex.The intermolecular hydrogen bonds and strongπ…πstacking interactions form a three-dimensional(3-D)supramolecular network.Solid-state photoluminescence spectrum reveals that it shows an emission in the blue region of the light spectrum.Time-dependent density functional theory(TDDFT)calculations reveal that this emission can be attributed to ligand-to-ligand charge transfer(LLCT).Solid-state diffuse reflectance data show that there is a narrow optical band gap of 1.83 eV.     

A Two-coordinate Copper(Ⅰ) Complex Constructed from Cyanuric Acid and 4,4′-Bipyridyl:Synthesis,Structure and Photoluminescence

A two-coordinate copper(Ⅰ)complex,Cu_2(bipy)(H_2L)_2(1)(H_3L=cyanuric acid,bipy=4,4'-bipyridyl),whichexhibits strong photoluminescence,has been synthesized under hydrothermal conditions and structurally character-ized by single crystal X-ray diffraction.The compound crystallizes in the monoclinic space group P2_1/n,with cellparameters:M_r=539.42,a=13.4806(5),b=4.5234(2),c=15.4952(8),β=105.526(3)°,V=910.39(7)~3,Z=2 and μ=3.52 mm~(-1).In the structure the two Cu(Ⅰ)ions are bridged by bipy to form a two-coordinate copper(Ⅰ)dimer.The adjacent dimer units are connected by hydrogen bonding interactions,resulting in 1D zigzag chainsalong the c axis.1 emits intense yellow light when excited with UV light.     

Synthesis,Crystal Structure and Magnetic Properties of a Coordination Polymer Based on Iron(Ⅱ) Carboxylate Helical Chains [Fe(bpdc)(H_2O)_2]n

A coordination polymer based on iron(II) carboxylate helical chains [Fe(bpdc)(H2O)2]n 1 has been constructed hydrothermally using H2bpdc (H2bpdc = 2,2'-bipyridine-4,4'-dicarboxylic acid), pyridine and FeSO4·7H2O. Its crystal structure reveals that the Fe(Ⅱ) ion adopts a slightly distorted octahedron. The carboxylates of bpdc ligands alternately bridge the Fe(Ⅱ) cations to form 1D infinite helical chains. The Fe···Fe intrachain distance is 4.8246(6) . The adjacent chains are further interlinked by the coordination of bpdc ligands and hydrogen bonding to form a 3D framework. Magnetic studies for complex 1 show weak antiferromagnetic coupling between the Fe(Ⅱ) ions. The best-fit for χM T vs. T with a Hamiltonian∑∑==iBiiHJSi SigHS11 leadsto g = 2.314(4) and J = -0.68(1) cm-1.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Synthesis and Structure Characterization of Aqua-（μ2-carbonato-O,O′）-（2,2′-bipyridyl）-copper（Ⅱ） Dihydrate

Under hydrothermal conditions the reaction of cis-aconitic acid with Cu2(OH)2CO3 and bipy (bipy = 2,2'-bipy) in H2O/DMF (3:2) afforded a neutral mononuclear compound [Cu- (bipy)((2-CO3)(H2O)](2H2O, which has been structurally characterized by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group Pī with a = 8.3950(5), b = 8.7974(5), c = 9.4496(3)（A。）, α = 98.270(3), β = 93.014(3), γ = 100.068(3)°, V = 677.83(6) （A。）3, Dc = 1.635 g/cm3, Z = 2, C11H14CuN2O6, Mr = 333.78, μ = 1.637 mm－1, λ(MoKα) = 0.71073 （A。）, F(000) = 342, the final R = 0.0616 and wR = 0.1273 for 1621 observed reflections with I > 2σ(I). The structure of the complex contains a distorted square pyramidal core with a bipy, a carbonate anion and a water molecule coordinating to a CuⅡ atom. The dihedral angle between the two planes composed of N(1)N(2)Cu(1) and O(1)O(3)Cu(1) is 21.73(8)°. The intermolecular hydrogen bonds (O…O) are observed in the crystal structure.     

Direct Electrochemical Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex: [(bipy)2Cu(PhCOO)]ClO4·(benzil) (benzil = 1,2-Diphenyl-ethane-1,2-dione)

A new mononuclear copper(Ⅱ) complex [(bipy)2Cu(PhCOO)]ClO4·(benzil) (bipy=2,2'-bipyridine, benzil=1,2-diphenyl-ethane-1,2-dione) was synthesized by direct electrochemical oxidation of Cu electrode in an acetonitrile solution with benzoic acid, 2,2'-bipyridine and benzoin. As soon as the current flowed in the cell, benzoin was oxidized to benzil quickly. The crystal structure was determined by X-ray diffraction. It belongs to monoclinic system, space group P21/c with a=14.860(2), b=20.784(3), c=11.9150(17) (A), β=101.401(3)°, V=3607.3(9) (A)3, Z=4, Mr=806.69, Dc=1.485 g/cm3, F(000)=1660, μ=0.742 mm-1, R=0.0788 and wR=0.1519 for 6254 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The complex contains a mononuclear [(bipy)2Cu(PhCOO)] cation, a solvate benzil molecule and a ClO4- anion which locates around the cation outside acting as the counter ion. The Cu(Ⅱ) ion is coordinated by two 2,2'-bipyridines and one benzoato ligand to form a distorted square-pyramid.     

Trihydrated Complex of Tetrabenzimidazole Copper(Ⅱ) Sulfate

A Trihydrated complex of benzimidazole copper(Ⅱ) sulfate [(C7H6N2)4CuSO4]·3H2O was synthesized and structurally characterized. The crystal structure of this compound is built up of six solvated water molecules and two dissimilar copper ions identified as Cu1 and Cu2. The coordination geometry of copper(Ⅱ) is a slightly distorted square pyramid. The four equivalent tertiary nitrogen atoms of the benzimidazole ligand form an equatorial plane, while the oxygen atoms of sulfato occupy the axial site. In the solid state, the title compound forms a three dimensional network structure via hydrogen bonds. The benzimidazole, sulfato ion and H2O moieties are connected by the intermolecular hydrogen bonds. The (EPR) spectrum shows axial symmetry with g⊥=2.039 and g∥=2.285. Variable temperature magnetic susceptibility shows that there is a weak antiferromagnetic interaction between the neighboring copper(Ⅱ) ions.     

苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

配位聚合物[Mn(4,4′-bpy)_(1.5)(H_2O)_3](ClO_4)·(4,4′-bpy)(L)·H_2O的水热合成和晶体结构(英文)

The title compound, [Mn(4,4'-bpy)1.5(H2O)3](ClO4)·(4,4'-bpy)(L)·H2O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm3, Z=2, Mr=780.10, Dc=1.375 g·cm-3, μ=0.483 mm-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4'-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4'-bipyridine molecules. CCDC: 615707.     

Hydrothermal Syntheses,Crystal Structures and Luminescence Properties of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on 2,2'-((Sulfonylbis(4,1-phenylene))bis(oxy))diacetic Acid

The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), namely [M2L2(4,4'-bipy)](M = Zn(1), Cu(2)). They have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction reveals that two complexes are isostructural and crystallize in orthorhombic system with space group Pbcn. All L^2- ligands bridge metal ions to form an infinite 1D Z-shaped chain along the a axis. Then through 4,4'-bipy, contiguous Z-shaped chains are linked to form a 2D layer structure. The luminescent studies of the H2L ligand and complex 1 in the solid state and thermogravimetric analyses(TGA) of two complexes are investigated.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

由4，4＇-联二吡啶桥联α,β-不饱和酸铜形成铜（II）的一维配位聚合物

A methanol solution of 4,4‘-bipyridine reacts with Cu2A4(H2O)2 to yield coordination polymers of general formula: [Cu2A4(bipy)]n [A: CH2=C(Me)CO2^- (1), CH2=CHCO2^- (2); bipy: 4,4‘-bipyridine]. They were characterized by elemental analyses, IR spectra and thermal analyses. The X-ray structure analyses of 1 show a one-dimensional chain structure where the binuclear structural units Cu2[CH2=C(Me)CO2]4 are bridged by 4,4‘-bipyridine molecules. Furthermore, the binuclear units between adjacent layers can form micropores. The temperature-dependent magnetic susceptibility of 1 indicates that the strong antiferromagnetic interaction exists between copper(Ⅱ) atoms in the binuclear units.     

A Two-coordinate Copper(I) Complex Constructed from Cyanuric acid and 4,4′-bipyridyl: Synthesis, Structure and Photoluminescence

A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/n, with cell parameters： Mr= 539.42, a= 13.4806（5）A↑°, b=4.5234（2） A↑°, c= 15.4952（8）A↑°,β = 105.526（3）°, V=910.39（7）A↑°^3, Z=2 and μ=3.52 mm^ -1. In the structure the two Cu（Ⅰ） ions are bridged by bipy to form a two-coordinate copper（Ⅰ） dimer. The adjacent dimer units are connected by hydrogen bonding interactions, resulting in 1D zigzag chains along the c axis. 1 emits intense yellow light when excited with UV light.     

Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn（PhCOO）2（4,4＇-bipyridine）]n

A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2)(A), V = 2074.42(7)(A)3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ＞ 2σ(Ⅰ). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.     

Synthesis and Structure of a Novel Copper（Ⅱ） Dinuclear Complex with 4,4′-Dipyridyl as the Bridge

With N,N′-bis(benzimidazol-2-methyl)amine as the ligand,a novel Cu(Ⅱ) dinuclear complex was synthesized as a mimetic compound of superoxide dismutase(SOD).The complex was characterized with element analysis,UV and IR spectra.The crystal structure was determined by using X-ray diffraction analysis.the crystal structure shows that Cu(Ⅱ) and its coordinated atoms construct distorted octahedron configuration with oxygen atome of (ClO4-)s in the axial directions.The coordinated cations are linked by (ClO4-)s to form nonplanar sheets.All sheets are linked together into three-dimensional network by the intermolecular hydrogen bonds.The result of the activity assay indicates that the complex does have certain biological activity.     

Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn(PhCOO)_2(4,4'-bipyridine)]_n

A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bi-pyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2) , V = 2074.42(7) 3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with I > 2σ(I). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is six-coordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.     

Hydrothermal Synthesis, Crystal Structure and Magnetic Property of a Novel Pentanuclear Copper(Ⅱ) Complex: [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5

The pentanuclear complex, [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5 (H3SIP=5-sulfoi-sophthalic acid), has been synthesized by the hydrothermal reaction of CuCl2 with NaH2SIP at 160 ℃, and characterized by single-crystal X-ray diffraction and IR spectrum. The crystal of the complex crystallizes in a trielinic system, space group P1, with a = 7.0018(5), b = 11.9725(8), c = 19.0424(13) A, α = 78.8540(10), β = 85.1710(10),γ = 83.6080(10)~, V = 1553.24(19) A3, Z = 1, C32H60O51S4Cu5, Mr= 1706.74, Dc= 1.825 g/cm3,μ = 1.937 mm-1, F(000) = 869, the final R = 0.0709 and wR = 0.1503 for 4235 observed reflections with I > 2σ(I). The five Cu2+ ions are connected by two symmetry-related tridentate SIP3- ligands and charge-balanced by two monodentate HSIP2- ligands, giving a discrete pentanuclear structure. The pentanuclear copper molecules are linked by hydrogen bonds to form a three-dimensional supramolecular structure. The temperature-dependent magnetic susceptibility data revealed weak ferromagnetic magnetic interactions between the Cu2+ ions.     

Synthesis and Crystal Structur of （4,4＇-H2bipy）[CdBr4]-H2O

The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms.