Syntheses,crystal structures,and quantum chemistry calculation of two Ni(Ⅱ)coordination polymers

Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.

Synthesis and Crystal Structure of a Cobalt(Ⅱ) Coordination Polymer with Benzene-1,3,5-triacetate and 1,4-Di(1H-imidazol-1-yl)benzene

A novel coordination polymer, [Co3 （bta）2（dib）2]·4H2O （1, H3bta=benzene-1,3,5-triacetic acid, and dib=1,4-di（1H-imidazol-1-yl）benzene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group Pī, with a=9.141（2）, b=9.667（2）, c=13.855（2）, α=100.83（3）, β=90.81（3）, γ=100.94（3）°, V=1179.0（4）3 , C48H46N8O16Co3 , Mr=1167.72, Dc=1.645 g/cm 3 , F（000）=599, μ=1.127 mm-1 and Z=1. The final R=0.0634 and wR=0.1703 for 4291 observed reflections （I 〉 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into a lamellar framework, which are further interlinked by the dib ligands to generate a binodal （3,8）-connected tfz-d net.

Synthesis and Crystal Structure of a Cobalt(Ⅱ) Coordination Polymer with Benzene-1,3,5-triacetate and 1,2-Di(pyridin-4-yl)ethene

A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687（15）, b = 11.2470（17）, c = 13.686（2） , α = 78.262（3）, β = 89.271（4）, γ = 81.292（3）°, V = 1425.2（4） 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F（000） = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections （I 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal （3,4,6）-connected （4.62）2（42.68.83.102）（64.82） net.

Synthesis,Crystal Structure and Magnetic Properties of a Cobalt(Ⅱ)Coordination Polymer with4,4'-(Propane-2,2-diyl)dibenzoate and4,4'-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.

Construction of a New Two-fold Interpenetrated Three-dimensional Cobalt(Ⅱ)Coordination Polymer Based on 2,5-Thiophenedicarboxylic Acid and Bis(imidazol-1-yl)methane

A cobalt coordination polymer, {[Co2（tdc）2（bimm）2]·（3 DMF）}n, was synthesized based on 2,5-thiophenedicarboxylic acid（H2 tdc） and bis（imidazol-1-yl）methane（bimm） mixed ligands. The asymmetric unit of the complex contains two Co2＋） cations, two tdc2-dianions, two neutral bimm ligands, and three free DMF molecules. In the complex, deprotonated tdc2-dianions alternately bridge the adjacent Co2＋ cations to generate chains, which are further connected by the flexible bimm ligands to form a 3 D structure containing adamantanoid-like subunits. In topology, the structure of 1 represents a 4-connected uninodal two-fold interpenetrated dia（66） topology. Moreover, the solid UV-Vis absorption spectra of the complex have also been investigated.

Two Cobalt(Ⅱ)Coordination Polymers Based on Tetrazylphosphonate and Tetrazylphosphonic Acid Ligands

Two cobalt coordination polymers with the same 2D structure have been hydrothermally synthesized based on two bifunctional ligands with tetrazole and phosphonate（phosphonic acid） groups,namely,diethyl 4-（2H-1,2,3,4-tetrazol-5-yl） benzylphosphonate（C_2H_5-L1） and 4-（2H-1,2,3,4-tetrazol-5-yl）benzylphosphonic acid（H_2L2）. The structures of the two complexes are characterized by elemental analysis,IR,TGA and X-ray single-crystal/powder diffraction. The pink block crystals of complex [Co（L1）（H_2O）]·H_2O（1） belong to the monoclinic system,space group C2/m with a = 20.8390（11）,b = 7.2695（3）,c = 10.0156（6） A,β = 109.773（7）°,V = 1427.80（13） A^3,Z = 4,D_c = 1.680 mg/cm^-3,M_r = 361.16,F（000） = 740,R = 0.0316 and wR = 0.0826 for 1702 observed reflections（I 〉 2σ（I））. The purple block crystals of complex [Co（L2）（H_2O）]·2H_2O（2） also belong to the monoclinic system,space group C2/c with a = 25.5382（16）,b = 7.3844（3）,c = 15.1925（11） A,β = 124.238（9）°,V = 2368.6（2） A^3,Z = 8,D_c = 1.969 mg/cm^-3,M_r = 351.12,F（000） = 1432,R = 0.0475,wR = 0.1617 for 2088 observed reflections（I 〉 2σ（I））. Both the nitrogen atoms of tetrazole group and oxygen atoms of phosphonate（phosphonic acid） groups in the ligands coordinated with the metal cobalt. The magnetic property of complex 1 is also investigated.

Construction of a Photocatalytic Cobalt(Ⅱ) Coordination Polymer with 4-Connected Diamond Topology

A novel cobalt（Ⅱ） coordination polymer, [Co（tdc）（bpmp）（H2O）]n（1）, was hydrothermally synthesized using 2,5-thiophenedicarboxylate（tdc） and bis（4-pyridylmethyl）piperazine（bpmp） ligand as the organic linkers. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic Cc space group, with a = 18.836（2）, b = 5.9540（7）, c = 20.414（2） A, β = 97.4300（10）°, V = 2270.1（5） A3, Z = 4, Mr = 515.44, Dc = 1.508 Mg/m^3, μ = 0.890 mm-1, F（000） = 1068, the final R = 0.0263 and w R = 0.0665 for 3714 observed reflections with I 2σ（I）. In compound 1, the Co（Ⅱ） ions are connected by tdc2- anions to form a 1D double chain, and such chains are further linked by bpmp ligands to form a three-dimensional（3D） structure. Topologically, the structure of 1 represents a uninodal 3D dia（6^6） topology. What＇s more, powder X-ray diffraction patterns and photocatalytic property for 1 have also been investigated.

Synthesis, Structure and Luminescent Property of a 2D Cd(Ⅱ) Coordination Polymer Based on Mixed-ligands of 1,3-Bis(imidazol)propane and Pyridine-3,5-dicarboxylic Acid

A new Cd（Ⅱ） coordination polymer, namely, [Cd（1,3-bip）（3,5-pdc）]n （1,3-bip = 1,3-bis（imidazol）propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid） has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178（7）, b = 1.72502（12）, c = 1.41635（6） ran, β = 92.653（4）°, V = 3.4212（3） nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F（000） = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd（lI） ions and each Cd（Ⅱ） attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.

A New 2D Zinc(Ⅱ) Coordination Polymer Constructed by Imidazole-4,5-dicarboxylic Acid(H_3IDC) and 1,4-Bis(imidazol-1-ylmethyl)-benzene(bix)

A new 2D Zn（Ⅱ） coordination polymer [Zn（HIDC）（bix）0.5]n（1） was obtained by the hydrothermal reaction of ZnCl2,imidazole-4,5-dicarboxylic acid（H3IDC） and 1,4-bis（imidazol-1-ylmethyl）-benzene（bix） with a 2：2：1 mole ratio.X-ray diffraction crystal structural analysis reveals it crystallizes in monoclinic,space group P21/n with a = 12.125（3）,b = 10.541（3）,c = 12.484（3） ,β = 115.834（4）°,V = 1436.0（6） 3,Mr = 338.60,Z = 4,Dc = 1.566 Mg·m-3,F（000） = 684,μ（MoKα） = 1.730 mm-1,the final R = 0.0439 and wR = 0.0888 for 2101 observed reflections with I ≥ 2σ（I）.In 1,each zinc（Ⅱ） ion is five-coordinated with a slightly distorted trigonal bipy-ramidal coordination geometry,and each μ2-HIDC2-acts as a bridge to bond two neighboring Zn（Ⅱ） ions,leading to a 1D zigzag chain architecture.The adjacent zigzag chains are further linked by μ2-bix to form an infinite 2D network structure.The fluorescence spectrum of 1 exhibits intense emission at 466 nm when excited at 397 nm in solid state at room temperature.

Urothermal Synthesis and Crystal Structure of a Zn(Ⅱ) Coordination Polymer with a 3-D Supramolecular Structure

A new metal-organic coordination polymer [Zn（hfipbb）（e-urea）]n（1,H2hfipbb = 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）,e-urea = ethylene urea） has been urothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction.The title complex crystallizes in monoclinic,space group P21/c with a = 13.302（4）,b = 10.981（3）,c = 13.804（4） ,β = 93.587（5）°,V = 2012.3（10） 3,C20H14N2O5F6Zn,Mr = 541.72,Z = 4,Dc = 0.447 g/cm3, = 0.328 mm-1,F（000） = 272,R = 0.0340 and wR = 0.1107 for 4528 observed reflections（I 〉2σ（I））.In the structure of compound 1,two Zn（Ⅱ） ions are bridged by two carboxylate groups from two hfipbb ligands to form a dinuclear unit,and each dinuclear Zn（Ⅱ） unit is linked with its two adjacent dinuclear units through four hfipbb ligands into an infinite one-dimensional double-chain.The interesting structural feature of compound 1 is that the one-D double-chains are self-interconnected into a three-D supramolecular structure through hydrogen bonds between the coordinated e-urea molecules and carboxylate oxygen atoms（N1 and O2,N2 and O4）.

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.

Two Isostructural 2-D Metal(Ⅱ)-organic Coordination Polymers from 4,4'-Bipyridyl and (E)-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic Acid

（E）-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic acid （H2mspda） is firstly employed in coordination chemistry.Two isostructural two-dimensional （2-D） 4-connected metal-organic coordination polymers with a general formula of {M2[（mspda）2（bpy）（H2O）2]}n （M=Zn（1） and Co（2）） are assembled from H2mspda,4,4＇-bipyridyl （bpy）,zinc and cobalt ions under hydrothermal conditions,and characterized by single-crystal X-ray diffraction analyses.Complex 1 crystallizes in monoclinic,space group P21/n with a=14.551（4）,b=10.941（3）,c=14.945（4）,β=98.817（4）o,V=2351.3（1）3,Dc=1.511 g/cm3,μ（MoKα）=1.090 mm-1,F（000）=1104,Z=4,the final R=0.0335 and wR=0.0485 for 3296 observed reflections （I 〉 2σ（I））.In compound 1,mspda2-spacers are only arrayed in a head-to-tail fashion which corresponds to a 2-D coordination polymer.Solid-state H2mspda and complex 1 have expected photoluminescence （λem=475～496 nm） at room temperature.

Hydrothermal Synthesis and Crystal Structure of One 3D Coordination Polymer of Cobalt(II) Achieved from 1,1′-Biphenyl-2,2′,6,6′-tetracarboxylic Acid Ligand

A new three-dimensional coordination polymer {[Co（BPTC）0.5（bix）]′（H2O）}n （1, H4BPTC = 1,1′-biphenyl-2,2′,6,6′-tetracarboxylic acid, bix = 1,3-bis（imidazol-l-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, and single-crystal X-ray analysis. The crystal is of orthorhombic, space group Pbcn with a = 13.2975（10）, b = 13.8424（12）, c = 22.6367（17） A, CoC22H19N4Os, Mr = 478.34, V = 4166.7（6） A3, Dc = 1.525 g/cm^3, F（000） = 1968,μ = 0.867 mm^-1, S = 1.023 and Z = 8. The final R = 0.0683 and wR = 0.1529 for 3655 observed reflections with I 〉 20（I）. In the title complex, the 2D Co-BPTC layer is formed through self-assembly of Co（II） ions and bridging BPTC4-ligands in a molar ratio of 2：1. The metal-organic lattice layers are further united together through the second bridging ligand bix to form a 3D metal-organic framework. The thermal stability of the title complex was studied by thermal gravimetric （TG） and differential thermal analysis （DTA）.

Synthesis,Crystal Structure,Thermal Stability,Luminescence and Magnetic Property of a New Mn^Ⅱ Coordination Polymer

One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(Hbtc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.

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 ℃.

Synthesis, Crystal Structure and Photoluminescence of a Zn(Ⅱ) Coordination Polymer Derived from 1,1'-Biphenyl-2,2',6,6'-tetracarboxylic Acid

A new polymeric znic（II） coordination polymer, [Zn2（bptc）·（H2O）4]n·nC H3 OH 1, was synthesized by the hydrothermal reaction of Zn（NO3）2·6H2O with 1,1＇-biphenyl-2,2＇,6,6＇-tetracarboxylic acid（H4bptc） and structurally characterized by single-crystal diffraction, IR and elemental analysis. The polymer crystallizes in the orthorhombic system, space group Pnna with a = 13.411（1）, b = 16.418（2）, c = 9.178（7）, V = 2025.2（3） 3, Z = 4, C17H14O13Zn2, Mr = 557.06, Dc = 1.827 g/cm3, F（000） = 1120, μ（MoK α） = 2.439 mm-1. The final R and wR are 0.0548 and 0.1691 for 1279 observed reflections with I 2（I）. In this compound, the bptc4- anion adopts monodentate bridging coordination modes connecting the zinc（II） ions to form a 1D chain structure, which furnishes a 2D supramolecular architecture through hydrogen bonding interactions formed by carboxylic oxygen atoms of bpdc, oxygen atoms of crystalline methanol and water molecules. Complex 1 displays an emissive maximum at 435 nm in the solid state at room temperature.

A New Co(Ⅱ) Coordination Polymer Based on a Flexible 1,4-Cyclohexanedicarboxylic Acid: Synthesis, Structure and Thermal Behavior

A new Co（Ⅱ） coordination polymer, [Co（1,4-chdc）（L）（H2O）]n（1）, was synthesized under hydrothermal condition（1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid, L = 2-（4-fluoro-phenyl）-1 H-imidazo[4,5-f][1,10]phenanthroline）. Its crystal structure was determined by single-crystal X-ray diffraction. 1 crystallizes in triclinic, space group P1 with a = 8.790（5）, b = 10.486（5）, c = 13.305（5） ?, α = 87.391（5）, β = 82.925（5）, γ = 81.841（5）o, V = 1204.2（10） ?3, Z = 2, C27H23FN4O5Co, Mr = 561.42, Dc = 1.548 g/cm3, F（000） = 578, μ（Mo Ka） = 0.769 mm-1, R = 0.0415 and wR = 0.1043. In 1, each 1,4-chdc anion bridges two neighboring Co（Ⅱ） atoms to give a chain structure. The L ligands are attached on one side of the chain through chelating the Co（Ⅱ） atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a double-chain structure. The double-chain structures are linked into a supramolecular layer structure through N–H···O hydrogen-bonding interactions between the adjacent double-chain structures. Moreover, the thermal behavior of 1 was also studied.

Construction of a Set of Cadmium(Ⅱ) Coordination Polymers with Atza and 2,2′-Bipy or 1,10-Phen Ligands (Atza=5-Aminotetrazole-1-acetato Anion)

Reactions of CdX2（X=NO3-, ClO4-） with Hatza （atza=5-aminotetrazole-1-acetato anion） and 2,2′-bipyridine （2,2′-bipy） or 1,10-phenanthroline （1,10-phen） in a methanol/aqueous solution produced a set of new Cd（Ⅱ） coordination polymers, {[Cd（atza）（H2O）（2,2′-bipy）]ClO4}n （1）, {[Cd（atza）（H2O）（1,10-phen）]ClO4 }n （2）, {[Cd（atza）（H2O）（2,2′-bipy）]NO3}n （3） and {[Cd（atza）2 （1,10-phen）]·0.5H2O}n （4）. Single-crystal X-ray diffraction analysis reveals that each Cd（Ⅱ） ion has a distorted octahedral coordination geometry in 1-4, and the Cd（Ⅱ） ion centers are connected through the tridentate atza bridging ligands to form a 2D layer （1-3） or ID chain （4） structure. The fluorescent properties of 2 and 4 are also discussed.

A Two-dimensional Anthracene-9,10-dicarboxylate Zinc(Ⅱ) Coordination Polymer Based on Binuclear [Zn_2Cl_2] Nodes: Synthesis, Characterization and Luminescent Properties

A two-dimensional（2D） 44 topological ZnⅡ coordination polymer {[Zn2Cl2（L）（4bpy）2]}∞（H2L = anthracene-9,10-dicarboxylic acid, 4bpy = 4,4ˊ-bipyridine） based on binuclear [Zn2Cl2] nodes has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction analysis. Moreover, the luminescent properties of the correspon- ding compound have been briefly investigated.

Ionothermal Synthesis, Crystal Structure and Photocatalytic Property of a New Cobalt Coordination Polymer

The reaction of flexible bis（imidazole） ligand and 1,2-bis（imidazol-l＇-yl）methane （bimm） with Co（Ⅱ） salt under ionothermal method resulted in the formation of a new coordination polymer {[Co（bimm）3]·（PF6）2}n （1）. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the triclinic Pi space group, with α = 8.647（6）, b = 12.092（9）, c = 14.967（1 l） A, α = 88.912（8）, β = 81.199（8）, ）, = 89.395（8）°, V= 1546 （2） A3, Z = 2, Mr = 793.39, Dc= 1.704 Mg/m3,μ = 0.768 mm-1 F（000） = 798, the final R = 0.0626 and wR = 0.1634 for 4319 observed reflections with I〉 2σ（I）. In compound 1, the Co（lI） ion is connected to another Co（ll） by two bimm ligands to form 1D double chains which are further linked by bimm ligands to form a 2D wavelike layer. Topologically, the structure of 1 represents a uninodal 2D 4-connected sq1/Shubnikov tetragonal plane net. Moreover, thermogravimetric analyses and photocatalytic property for 1 have also been investigated.