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.

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.

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, 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.

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.

Synthesis, Crystal Structure and Magnetic Properties of a Novel Azide-bridged Copper(Ⅱ) Coordination Polymers Containing Nitroxy Nitroxide

A novel azide-bridged copper（Ⅱ） coordination polymer, [Cu3（NITpPy）4（N3）6]n （NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl）, was structurally and magnetically characterized. It crystallizes in the triclinic space group P with a = 7.6932（10）, b = 14.5556（19）, c = 16.122（2） , α = 108.443（2）, β = 95.251（2）, γ = 104.236（2）°, V = 1631.7（4） 3, C48H64Cu3N30O8, Mr = 1379.87, Z = 1, Dc = 1.404 g/cm3, μ（MoKα） = 1.041 mm-1, F（000） = 713, the R = 0.0510 and wR = 0.1185 for 4285 observed reflections with I 2σ（I）. X-ray analysis reveals that the Cu（Ⅱ） ions are linked by nitrogen atom of μ1,1 azido ligands to form a Cu-Cu-Cu unit. The units are linked by μ1,3 azido ligands through a bridging style to form a one-dimensional coordination polymer. The variable-temperature magnetic susceptibility data of the complex show ferromagnetic interactions in the complex.

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles)Ligands

Two compounds have been obtained by the reaction of metal（Cu（II））, 4,4＇-bis（imidazol-l-yl）diphenyl thioether（BIDPT） with two carboxylic acids, 4,4＇-oxydibenzoic acid（H2oba） and phthalic acid（H2pht）. The crystal structures of the resulting compounds, namely {[Cu（BIDPT）（oba）]·H2O}n（1） and {Cu（BIDPT）（pht）}n（2）, have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310（3）, b = 10.7791（1）, c = 19.3913（2）A, V = 5817.0（3） ？3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678（2）, b = 11.0259（1）, c = 22.906（2） A, β = 97.727（2）o, V = 4571.8（8） A3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional（2D） wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.

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 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.

Synthesis Characterization Non-isothermal Kinetics of the Thermal Decomposition and Redox Properties Derived from Copper(Ⅱ) Binuclear Coordination Compound of 1,4-Bis-(1'-Phenyl-3'-Methyl-5'-Pyrazolone-4')-1,4-Butanedione

The paper reports the synthetic procedure and character of Copper(II) binuclearcoordination compound of 1,4-bis-(1'-phenyl-3'-methyl-5'-pyrazolone Thenon-isothermal kinetics of thermal decomposition of the complex has been stUdied from the TG-DTGcurves by means of the Achar et al. and Coats-Redfern methods,the most probab1e kinetic equation canbe expressed as dofdtrAe -E / RT * l /(2Q).The corresponding kinetic compensation effect expressions arefound to be lnuA=0. 1794E+0. 1689.The non-isothermal thermal decomposition process of the complex isone-dimensional diffusion.But electrochemical studies of the complex(Cu2L'2)from cyclic voltamrnetriccurves by means of powder microelectrodes technique'',shows one two-electron irreversible process.

Cis-and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper(Ⅱ) and Silver(Ⅰ)

After the preparation of 1,4-bis（4,5-dihydro-lH-imidazol-2-yl）benzene（bdib）, a nitrogen heterocycle with potential coordination manners of both cis- and trans-configuration forms, three complexes, including cis-[Cuz（bdib ）2（/L-OCH3）2]Cl2·2MeOH（1）, trans-[Cu（bdib）（AcO）2]n（2）, and cis-[Ag2（bdib）2]（NO3）2.2H20（3）, were successfully self-assembled. Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with P1 space group.

Relationship between Coordination Structure and Biological Activity of Copper(II) Nicotinate

The copper（Ⅱ） complexes of pyridine-3-carboxylic acid （nicotinic acid） and pyridine-2-carboxylic acid （isonicotinic acid） were synthesized, and their structures were characterized by elemental analysis, infrared spectrum, powder X-ray diffraction and so on. The results show that under experimental conditions, the ligands of synthesized copper nicotinate and copper isonicotinate are coordinated simultaneity with copper（Ⅱ） via the nitrogen of pyridine group and an oxygen of carboxylic acid group to form bidentate chelates. The crystal of copper nicotinate with two six-membered chelate rings belongs to monoclinic system, while that of copper isonicotinate having two five-membered chelate rings is of triclinic system. The tests show that the biological activities, such as the improvement of feed utilization, growth, anti-oxidation ability of organism and disease-resistant power, are different when copper nicotinate, copper inicotinate, copper-lysine chelate, copper-methionine chelate and copper sulphate are added in pig＇s feed, respectively. Due to its higher biological activity, less pollution and lower toxicity, copper nicotinate has wide potential applications as a feed additive.

Hydrothermal Synthesis and Crystal Structure of a Square Grid Coordination Copper(II) Polymer from 1,4-Bis(imidazole-1-ylmethyl)benzene

The title compound [Cu（bix）2（NO3）z·H2P]n 1 （bix = 1,4-bis（imidazole-1-ylme-thyl） benzene） has been synthesized by hydrothermal method. Its crystal structure is of monoclinic, space group P1^- with a = 8.3075（13）, b = 9.4725（13）, c = 10.0192（13） A, α = 91.088（4）, β = 104.063（6）, γ = 101.88（1）, V = 746.5（3） A^3, Z = 1, C28H30N10O7Cu1, Mr = 682.16, Dc = 1.518 g/cm^3, μ = 0.796 mm^-1, F（000） = 353, the final R = 0.0535 and wR = 0.0996 for 2921 observed reflections with I 〉 2σ（I）. Each bix ligand binds two Cu（Ⅱ） ions to form a 2-D（4,4） square grid layer, which is connected by hydrogen bonds showing large channels occupied by solvated water molecules and nitrate anions.

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.

COORDINATION CROSSLINKING OF NITRILE RUBBER FILLED WITH COPPER SULFATE PARTICLES

By incorporating copper sulfate （CuSO4） particles into acrylonitrile butadiene rubber （NBR） followed by heat pressing, a novel vulcanization method is developed in rubber through the formation of coordination crosslinking. This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber. No other vulcanizing agent or additional additive is involved in this process. By analyzing the results of DMA, XPS and FT-IR, it is found that the crosslinking of CuSO4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups （-CN） and copper ions （Cu^2＋） from CuSO4. SEM and EDX results revealed the generation of a core （CuSO4 solid particle）- shell （adherent NBR） structure, which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover, poly（vinyl chloride） （PVC） and liquid acrylonitrile-butadiene rubber （LNBR） were used as mobilizer to improve the coordination crosslinking of CuSO4/NBR. The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization. In addition, crystal water in CuSO4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO4 and promoted the metal ionization.

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.

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.

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）.

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.