Crystal Structure, Electrochemical and Fluorescent Properties of a New Copper(Ⅱ) Coordination Polymer with 2,3-Pyridinedi-carboxylic Acid

A new copper(Ⅱ)coordination polymer[Cu5(Hpt)5(H2O)2(2,3-PCA)2]n·12nH2O(1)has been successfully synthesized under hydrothermal conditions with copper hydroxide,3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and 2,3-pyridinedi-carboxylic acid(2,3-PCA).The structure of the title compound was determined by X-ray diffraction analyses,elemental analyses and IR spectrum.The architecture of 1 consists of one-dimensional sandwich-like chains which are connected by extensive hydrogen bonding interactions.The solid-state photoluminescence displays an obvious emission band at 384 nm upon excitation at 340 nm.In addition,electrochemistry property has also been studied.

Temperature-controlled Hydrothermal Synthesis of Copper(Ⅰ or Ⅱ) Coordination Polymers via a Variety of Copper Coordination Modes

Two 1D coordination polymers Cu2I（C6N3H4）2（1） and CuⅡ（C6N3H4）2·H2O（2） based on benzotriazole（Bta） were hydrothermally synthesized by controlling the crystallization temperature.Single-crystal X-ray diffraction（XRD） analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {―Cu―N=N―N―} n,where the Cu（I） ions adopt linear,triangular,and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain.For compound 2,the Cu（Ⅱ） ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains,which stacks through π-π interactions to construct a 2D layer structure.Further characterizations including elemental analyses,infrared IR spectra,thermogravimetric（TG） analyses and luminescence properties have been done.

Crystal Structure, Thermal Behavior and Luminescence of a New Copper Coordination Polymer Constructed with 4-(Carboxymethoxy)-benzoic Acid

A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.

Synthesis and Crystal Structure of a Co(II) Coordination Polymer Derived from a Flexible Bipyridyl Derivative Ligand

The self-assembly of a flexible bipyridyl ligand 2,2?-bis(4-pyridylmethyle- neoxy)-1,1?-biphenylene (4,4?-bpp) with cobalt(II) center gave rise to a one-dimensional chain complex [Co(μ-4,4?-bpp)2(SCN)2?H2O]n 1 which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in monoclinic, space group C2/c with unit cell parameters: a = 13.1888(13), b = 24.230(2), c = 15.4218(17) ?, β = 93.291(6)o, V = 4920.1(8) ?3, Z = 4, C50H42CoN6O5S2, Mr = 929.95, Dc = 1.255 g/cm3, F(000) = 1932 and μ(MoKα) = 0.484 mm-1. The final R and wR are 0.0691 and 0.1670 for 3746 observed reflections with I > 2σ(I). 1 possesses an infinite 1-D polymeric chain structure consisting of the repeated basic square units Co2(μ-4,4?-bpp)2, where the Co(II) center acts as the joint of the square ring. The Co(II) center is coordinated in a slightly distorted octahedral geometry with four nitrogen atoms from four different 4,4?-bpp ligands in the equatorial plane and two trans thiocyanate ligands occupying the axial positions, preventing the formation of an extended framework.

Hydrothermal Synthesis, Crystal Structure and Properties of a New Copper Coordination Polymer [Cu2I（C7H5N4）2]n with 3-（Pyridin-2-yl）-1,2,4-triazole) Ligand

A new copper coordination polymer[Cu2I(C7H5N4)2]n(1)with the 3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and copper iodide was synthesized.It crystallizes in the triclinic space group P1 with a=8.6380(9),b=9.2434(9),c=11.8588(12)A,α=99.5890(10)o,β=109.0990(10)o,γ=105.2800(10)o,V=829.25(15)A^3,Dc=2.180 g/cm3,Z=2,F(000)=522,GOOF=1.046,the final R=0.0245 and wR=0.0598.The crystal structure shows that two copper ions are bridged by twoμ2-η1:η0-3-(pyridin-2-yl)-1,2,4-triazole anions and two iodide ions.The coordination environments of the Cu ion are Cu(1)N5 and Cu(2)N2I2,giving distorted square pyramidal geometry and trigon pyramid geometry.The magnetic and fluorescent properties of 1 were studied.

Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756（10）,b= 1.57756（10）,c=2.1438（3）nm,V=5.3352（8） nm^3,Dc=1.524 g/cm^3,Z=4,F（000）=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper（1） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry; the copper（2） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.

A Novel 3D Cd(II) Coordination Polymer with an Unusual 3-Connected(8~2·10) Lig Net: Synthesis, Crystal Structure and Luminescent Properties

A new 3D Cd(II) coordination polymer, [Cd(Hpidc)]n(1, H3 pidc = 2-(pyrid-2-yl)-1H-imidazole-4,5-dicarboxy acid), has been prepared and characterized by elemental analysis, IR spectra, PXRD, and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group Fdd2 with a = 22.833(9), b = 25.536(9), c = 7.437(3) A, V = 4336(3) A3, Z = 16, Dc = 2.105 Mg·m-3, μ = 2.025 mm-1, F(000) = 2656, and the final R = 0.0261 and w R = 0.0636. The structure determination reveals that 1 exhibits a rare 3D 3-connected lig net with a point symbol of(82·10). In addition, the solid state properties such as thermogravimetric analysis and luminescence of 1 were also studied.

Hydrothermal Synthesis, Crystal Structure and Thermal Analyses of Pyrazine-2,3-dicarboxylic Acid Bridged Co(II) Coordination Polymer of _∞~2[Co(phen)(μ-L)_(3/3)]·H_2O (H_2L = Pyrazine-2,3-dicarboxylic Acid)

A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex 2 ∞ [Co- (phen)(μ-L)3/3]?H2O (H2L = pyrazine-2,3-dicarboxylic acid) has been hydrothermally synthesized, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group P21/n with a = 11.480(2), b = 11.885(2), c = 12.939(3) ?, β = 110.55(3)°, V = 1653.1(6) ?3, Mr = 423.25, Dc = 0.425 g/cm3, Z = 4, R = 0.0361 and wR = 0.1011. The title complex consists of 2D 2 ∞ [Co(phen)(μ-L)3/3] layers and crystal water molecules. Each Co atom is octahedrally coordinated by three N atoms and three O atoms to form 2D 2 ∞ [Co(phen)(μ-L)3/3] polymeric layers. Furthermore, such 2D layers are stacked into 3D supramolecular frameworks via Van der Waals’ intermolecular forces, strong and weak hydrogen-bond interactions. The coordination phen and crystal water molecules are resided into cavities of the frameworks.

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 synthesized by the reaction of mellitic acid and Cu（CH3COO）2·H2O in the presence of base. Crystallographic data for 1： C12H8O16Cu3, Mr = 598.80, orthorhombic, Pbcn, a = 8.4378（6）, b = 10.0396（7）, c = 17.6799（12）A, V = 1497.70（18）A^3, Z = 4, De = 2.656 g/cm^3, 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, Crystal Structure, Thermal Stability and Solid UV-Vis Absorption Spectra of One New Copper(Ⅱ) Coordination Polymer

A new coordination polymer [Cu2(OH)(nbta)(tib)(H2 O)2]n(1, H3 nbta = 5-nitro-1,2,3-benzenetricarboxylic acid, tib = 1-(4 H-1,2,4-triazol-4-yl)-4-(imidazol-1-yl)benzene) constructed from dimeric Cu(Ⅱ) units has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis. The compound crystallizes in monoclinic system, space group I2/c, with a = 17.8474(9), b = 11.7588(6), c = 21.9221(11) ?, β = 104.419(5)°, V = 4455.7(4) ?3 and Z = 8. Compound 1 is a three-dimensional structure constructed from dimeric Cu(Ⅱ) units and presents a 2-nodal(3,5)-connected net. Moreover, the thermal stability and solid UV-Vis absorption spectra have been investigated.

A New Copper Coordination Polymer with Magnetic Property Based on 3-(1,2,4-Triazol-1-yl)benzoic Acid

A copper coordination polymer, namely [CuL2（H2O）2]·H2O 1（HL = 3-（1,2,4-triazol-1-yl）benzoic acid） has been synthesized by the hydrothermal reaction under 140 ℃. The structure of 1 was characterized by single-crystal X-ray diffraction analysis, elemental analyses, powder X-ray diffraction, IR spectroscopy, and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that 1 crystallizes in P21/n space group with a = 12.374（5）, b = 12.730（5）, c = 12.561（5） A°, β = 91.105（9）o, V = 1978.2（14）A°^3, Z = 4, Dc = 1.618 g/cm^3, μ = 1.160 mm^-1, F（000） = 964, the final R = 0.0449 and w R = 0.1443 with I 〉 2σ（I）. Magnetic measurements show that 1 exhibits antiferromagnetic interactions by the analysis of magnetic test data.

Synthesis, Structure and Magnetic Property of a New Three-dimensional Copper(Ⅱ) Coordination Polymer Constructed from 5-Tert-butyl Isophthalic Acid and N-donor Ligand

A new 3D copper（Ⅱ） coordination polymer, {[Cu_2（tbip）_2（1,3,5-tib）]×2H_2O}n（1, H_2 tbip = 5-tert-butyl isophthalic acid, 1,3,5-tib = 1,3,5-tris（1-imidazolyl）benzene）, has been synthesized by hydrothermal reaction of Cu（OAc）_2·4H_2O, H_2 tbip and 1,3,5-tib. It has been structurally characterized by element analysis, IR and magnetic measurement. X-ray single-crystal analysis was carried out for 1, which crystallizes in the triclinic system, space group P1 with a = 7.822（3）, b = 15.854（6）, c = 17.553（6） ？, a = 113.033（4）, β = 90.694（4）, g = 101.006（4）°, V = 1957.3（12） ？~3, Z = 1, D_c = 1.493 g/cm^3, M_r = 1759.70, F（000） = 908, R = 0.0721 and w R = 0.1978 with I 〉 2s（I）. The single-crystal X-ray diffraction studies reveal that compound 1 exhibits 2D [Cu（tbip）] layers which are further pillared by 1,3,5-tib ancillary ligand with terminal tridentate coordination mode to generate the final 3D structure. Magnetic susceptibility data for 1 have been measured in the range of 2~300 K. There are antiferromagnetic interactions between copper ions of the compound.

A One-dimensional Coordination Polymer of Copper(Ⅱ) and Bis(4,6-dimethyl-2-pyrimidinethiolato)methane

Reaction of bis（4,6-dimethyl-2-pyrimidinethiolato）methane（bpytm） with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2（μ-bpytm）]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433（5）,b=13.6986（4）,c=7.8434（2）,β=100.371（2）°,V=1790.71（9）3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ（MoKα）=1.751mm-1,F（000）=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ〉2σ（I） and 206 variables. The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms. Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry. The average Cu-N and Cu-CI bond lengths are 2.025（2） and 2.234（1） A, respectively.

A 2D Brickwall-like Copper(Ⅱ) Coordination Polymer Based on Phenyliminodiacetate and 4,4?-Bipyridine: Synthesis,Crystal Structure and Magnetic Property

A novel copper（II） coordination polymer of {[Cu3L2（4,4＂-bipy）4]（CIO4）2＂20H20}, （1） was synthesized by the reaction of H2L （C6HsN（CH2COOH）2, phenyliminodiacetic acid）, CuSO4.5H20, NaCIO4.H20 and 4,4＂-bipy （4,4＂-bipyridine） in water/methanol, followed by slow evaporating at room temperature. The compound was characterized by elemental analysis （EA）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and single-crystal/powder X-ray diffraction. The result of single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic crystal system with C2/c space group, a = 2.9974（4）, b = 1.7270（2）, c = 2.0007（3） nm, fl = 128.793（2）°, V= 8.0722（19） nm3, Z = 4, Dc = 1.472 g.cm-3,/a = 0.942 mm-1, F（000） = 3716, R= 0.0487 and wR = 0.1204 （I 〉 20（/））. The basic structural unit of 1 is a trinuclear cluster unit of [Cu3L2]2＋, which is constructed by two #2-L2- ligands bridging and chelating three Cu（Ⅱ） ions. These [Cu3L2]2＋ units are connected with each other by 4,4＂-bipy ligands to generate a 2D cation brickwall-like network of [Cu3L2（4,4＂-bipy）4]n2n＋. These adjacent 2D cation layers are further stacked in a staggered fashion via interlayer stacking interactions to form a 3D supramolecular structure with 1D open square channels, in which the C104- counter anions and lattice water molecules are filled. Furthermore, the magnetic property of 1 was also investigated.

A 2-D Copper Coordination Polymer[Cu(4,4'-bpy)(H_(2)O)_(4)](C_(4)H_(2)O_(4))(H_(2)O)_(4)Integrated by Hydrogen Bonds and VDW Interactions

The title compound, [Cu(4,4-bpy)(H2O)4](C4H2O4)(H2O)4 1, has been syn- thesized by the reaction of Cu(NO3)23H2O with 4,4-bipyridine and fumaric acid, and structurally characterized by X-ray diffraction analysis. Its crystal structure belongs to monoclinic, space group C2/c with a = 16.6350(5), b = 11.1667(2), c = 13.1371(4) ? = 125.144(1), C14H26CuN2O12, Mr = 477.91, Z = 4, V = 1995.47(9) 3, Dx = 1.591 g/cm3, m = 1.160 mm-1, F(000) = 996, R = 0.0331 and wR = 0.0883 for 1765 observed reflections (I > 2(I)). A two-dimensional network is formed in complex 1 through the hydrogen bonds and VDW interactions.

Synthesis and Crystal Structure of a 1D Chained Coordination Polymer Containing One-dimensional Egg-like Channels:{[Cu_2(C_2O_4)_2(inta)_4](inta)}_n (inta=Isonicotinamide)

A new one-dimensional copper coordination polymer chain has been prepared and fully characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound { [Cu2（C2O4）2（inta）4]（inta）}n 1 crystallizes in the triclinic system, space group P1, with a = 8.4722（5）, b = 10.9825（6）, c = 11.6128（6）A, α= 104.8050（10）,β = 102.5740（10）, γ= 109.6890（10）°, V= 927.18（9） A3, Mr = 929.79, Z = 1, Dc = 1.665 g/cm^3, F（000） = 475, μ = 1.231 mm^-1, R = 0.0453 and wR = 0.1185 for 3290 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Of the compound, the Cu center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the copper atom and each inta serving as a terminal ligand by employing only one N-donor to coordinate with the Cu center. An infinite {Cu2（C2O4）2}∞ chain is formed along the c axis. Furthermore, the 1D chains are held together via extensive hydrogen-bonding interactions to generate a three-dimensional network with 1D channels （ca. 5.491A×11.507A） where inta molecules are filled.

Crystal Structure of a Two-dimensional Coordination Polymer [Ba_2(phen)_4(tp)_2]_n

A novel two-dimensional coordination polymer [Ba2（phen）4（tp）2]n （phen = 1,10- phenanthroline, tp = terephthalic acid） has been synthesized with tp as bridge ligands and structurally determined by X-ray crystallography. The crystal belongs to the monoclinic system, space group C2/c, with a = 18.877（4）, b = 18.489（4）, c = 15.658（3） A, β = 103.61（3）°, V= 5311.5（19）A^3, C32H20O4N4Ba, Mr = 661.86, Z= 8, F（000） = 2624,μ= 1.542 mm^-1, Dc= 1.655 g/cm^3, the final R = 0.0228 and wR = 0.0554 for 6063 observed reflections （I 〉 2σ（I））. The structural analysis shows that each tp ligand bridges barium atoms to form a two-dimensional infinite layer. There are aromatic π-π stacking interactions between neighboring layers, and aromatic π-π interactions further extend such layers into a three-dimensional supramolecular framework.

A Novel Two-dimensional Lead(Ⅱ) Coordination Polymer Based on Dinuclear Lead(Ⅱ) Unit Containing(5-Chloro-quinolin-8-yloxy) Acetate

A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603（7）, b = 8.6907（4）, c = 8.4745（3）A, β = 101.1110（11）°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25（9）A3, Z = 4, Dc = 2.628 g/cm^3, F（000） = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead（II） cation, one（5-chloro-quinolin-8-yloxy）acetate（L） ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit（SBU） and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079（1）A. The fluorescence emission peak of complex 1 appears near 407 nm.

A New Two-dimensional Copper(II) Complex with p-PhDTA Bridges

A new p-PhDTA bridged Cu（II） complex [Cu2（p-PhDTA）（DMSO）2]·4DMSO （p-PhDTA = p-phenylenediamine-N,N,N,N＇-tetraacetic acid） has been synthesized and structurally characterized. The crystal belongs to orthorhombic, space group Pca21 with a = 19.572（4）, b = 19.552（4）, c = 10.156（2）A, C26H48N2O14CU2S6, Mr = 932.10, V = 3886.4（13）A3, Z = 4, Dc = 1.593 g/cm^3, F（000） = 1936, λ（MoKa） = 0.71073A,μ = 1.480, R = 0.0487 and wR = 0.1151 for 8464 observed reflections （I 〉2σ（I））. In the complex, the oxygen atoms of carboxylate of p-PhDTA connect the Cu atoms in a syn-anti type, giving one-dimensional chains which are further linked by the benzene groups ofp-PhDTA to form a novel two-dimensional structure.

Syntheses, Structures and Properties of Two 2D Coordination Polymers from 5-(Pyridin-2-yl-methyl)aminoisophthalate

Hydrothermal reactions of 5-（pyridin-2-yl-methyl）aminoisophthalic acid（H2paip） with Mn（OAc）2·4H2O and Cu（NO3）2·3H2O produced two 2D complexes, [Mn（paip）]n·nH2O（1） and [Cu（paip）（H2O）]n（2）. In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn（Ⅱ） into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu（Ⅱ） into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250 ℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.