Hydrothermal Synthesis,Crystal Structure,Spectrum Properties and Quantum Chemical Calculation of a Trinuclear Copper（Ⅱ） Complex with 3-（Pyridin-2-yl）-1,2,4-triazole

A three-dimensional framework copper(Ⅱ) coordination polymer with copper carbonate basic and 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) has been hydrothemally synthesized.The complex (2,C14 H10 CuN8 ·3H2 O) crystallizes in tetragonal,space group P4 2 /n,a=2.08581(12),b=2.08581(12),c=0.72331(4) nm,M r=761.73,V=3.1468(3) nm 3,Dc=1.608 g/cm 3,Z=4,F(000)=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.     

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) nm3,Dc=1.524 g/cm3,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 Thermal Stability of Complex [Cu（C_（14）H_（10）O_4）（C_（12）H_8N_2）_2]·2H_2O

The title complex has been synthesized with 2,2'-biphenyl dicarboxylic acid and 1,10-phenanthroline(phen)in the solvent mixture of water and methanol.It crystallizes(C38H28CuN4O6,Mr = 700.1)in triclinic,space group P1 with a = 1.0868(2),b = 1.2175(2),c = 1.6206(3)nm,α = 110.161(2),β = 102.605(3),γ = 93.667(2)o,V = 1941.6(6)nm3,Dc = 1.198 g/cm3,Z = 2,F(000)= 722,R = 0.0558 and wR = 0.1208.The crystal structure shows that the copper atom is coordinated with one oxygen atom from 2,2'-bphenyl dicarboxylic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules,forming a distorted square-pyramidal coordination.The TG analysis shows that the title complex is stable under 160.0 ℃.     

Synthesis, Crystal Structure and Fluorescent Property of One New Complex [Na2（2-benzoylbenzoato）4（Phen）2（H2O）2]·H2O

One binuclear sodium(Ⅰ) complex [Na2(2-benzoylbenzoato)4(Phen)2(H2O)2]·H2O has been synthesized with 2-benzoylbenzoic acid and 1,10-henanthroline as ligands. The crystal structure was determined by X-ray diffraction. The crystal belongs to the triclinic system with space group P , a = 1.08096(8), b = 1.09619(8), c = 1.09740(8) nm, α = 79.0600(1), β = 71.0450(1), γ = 62.0540(1)o, V = 1.08533(1) nm3, Dc = 1.421 g/cm3, Z = 2, F(000) = 484, GOOF = 1.036, the final R = 0.0363 and wR = 0.0961. The crystal structure shows that two neighboring sodium(Ⅰ) ions are linked together by two bridging water molecules, and each end position is coordinated with one 1,10-phenanthroline molecule and one 2-benzoylbenzoato to form a binuclear structure. Each sodium(Ⅰ) ion in the molecule is coordinated with five atoms to give a distorted trigonal bipyramid. The fluorescence property of the title complex is also discussed.     

Synthesis, Crystal Structure and Thermal Stability of a Nickel（Ⅱ） Complex with Bicycle[2.2.1]-2-hepten-5,6-dicarboxylic Acid

The nickel complex {Ni(2,2-bipy)(H2O)3[C8H11O2(COO)]}(H2O)3 with bicycle-[2.2.1]-2-hepten-5,6-dicarboxylic acid [C7H8(COOH)2] and 2,2'-bipyridine (bipy) as ligands has been synthesized and characterized. It crystallizes in monoclinic, space group P , with a = 0.74975(3), b = 1.20309(4), c = 1.30593(4) nm, α = 109.861(2), β = 98.519(2), γ = 90.575(2)o, V = 1.09337(7) nm3, Dc = 1.552 g/cm3, Z = 2, F(000) = 524, the final GOOF = 1.064, R = 0.0397 and wR = 0.1171. The crystal structure shows that the nickel ion is coordinated with four oxygen atoms from one bicycle[2.2.1]-2-hepten-5,6-dicarboxylic acid molecule and three water molecules and two nitrogen atoms from the 2,2′-bipyridine molecule, forming a distorted octahedral coordination geometry. The result of TG analysis shows that the title complex is stable under 200.0 ℃.     

Synthesis,Crystal Structure and Properties of a Copper Complex with the Bicycle[2.2.1]-2-heptene-5,6-dicarboxylic Acid

A new copper complex 2{Cu(C10H8N2)[C8H11O2(COO)](H2O)3}·(H2O)5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid(H2L) [C7H8(COOH)2], basic copper carbonate and 2,2'-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a = 7.4626(5), b = 11.9779(8), c = 12.9841(8), α = 109.7040(10), β = 98.7550(10), γ = 90.6240(10)o, V = 1077.50(12)3, Dc = 1.538 g/cm3, Z = 1, F(000) = 520, GOOF = 1.065, R = 0.0360 and wR = 0.0950. The copper ion is coordinated with four oxygen atoms from one H2 L molecule and three water molecules together with two nitrogen atoms from the 2,2'-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Complex Cu(o-Methylbenzoic acid)_2(2,2′-bipy)·(H_2O)

The title complex (C26H24CuN2O5, Mr = 508.01) has been synthesized by o-me- thylbenzoic acid, 2,2′-bipyridine (bipy) and copper perchlorate in the mixed solvent of water and methanol. It crystallizes in orthorhombic, space group P212121 with a = 0.70814(10), b = 1.6953(3), c = 1.9539(3) nm, V = 2.3457(6) nm3, Dc = 1.439 g/cm3, Z = 4, μ = 0.971 mm-1, F(000) = 1052, R = 0.0432 and wR = 0.0860. The structural determination shows that the copper atom is coordinated by three oxygen atoms from two o-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The cyclic voltammetric behavior of the complex is also discussed.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Mn2（phen）2（p-CBA）4（H2O）

One novel complex Mn2(phen)2(p-CBA)4(H2O) has been hydrothermally syn- thesized from p-chlorobenzoic acid (p-CBA), 1,10-phenanthroline (phen) and anhydrous man- ganese(Ⅱ) sulfate and then characterized. Crystal data for this complex: monoclinic, space group C2/c, with a = 2.3416(3), b = 1.5604(2), c =1.5605(2) nm, β = 121.048(2)o, V = 4.8849(12) nm3, Dc = 1.510 g/cm3, Mr = 555.26, Z = 8, μ = 0.798 mm-1, F(000) = 2256, GOOF = 1.032, the final R = 0.0393 and wR = 0.0816. The crystal structure shows that two neighboring manganese(Ⅱ ) ions are linked together by two bridge-chelating p-chlorobenzoic groups and one bridging water molecule, forming a cage structure with the Mn–Mn bond distance of 0.3512 nm. Each manganese(Ⅱ ) ion is coordinated by two nitrogen atoms of one 1,10-phenanthroline molecule and four oxygen atoms from three p-chlorobenzoic acid anions and one water molecule, giving a distorted octahedral coordination geometry. The cyclic voltammetric behavior of the complex was also investigated.     

Crystal Structure and Thermal Stability Properties of a New 1D Chain Cu（ll） Coordination Polymer with 2,3-Pyridinedicarboxylic Acid as the Ligand

A new 1D chain copper coordination polymer [CuE（H2L）2（C10HsN2）（HEO）2]n＇3n（H20） with 2,3-pyridinedi carboxylic acid （H2L） and 2,2＇-bipyridine （2,2＇-bipy） as ligands has been synthesized in the mixed ethanol and water solvents. Crystal data for this complex are as follows： monoclinic, space group P2Jc, a = 7.7713（7）, b = 27.478（3）, c = 13.2621（13）/1,, fl = 100.6940（10）, V= 2782.8（5） A3, Dc = 1.722 g/cm3, Z = 4, p = 1.61 mm-1, F（000） = 1472, the final R = 0.0363 and wR = 0.0933. In the crystal structure, the whole molecule consists of two cooper ions, two H2L, one 2,2＂-bipy molecule and six water molecules. Each central copper ion is coordinated with three oxygen atoms from two H2L and one water molecule, two nitrogen atoms from one 2,2＇-bipy molecule and two H2L, giving a distorted tetragonal pyramidal geometry. Thermal stability properties of the complex were investigated.     

Synthesis,Crystal Structure and Fluorescent and Thermal Stability Properties of the Zinc(Ⅱ) Complex [Zn(C_(15)H_(11)O_3)_2(C_(12)H_8N_2)_2]·5H_2O

A new complex has been synthesized with o-methylbenzoyl-benzoic acid(HL) and 1,10-phenanthroline(phen) in the mixture of water and ethanol. It crystallizes in monoclinic, space group C2/c with a = 13.6328(18), b = 17.7876(18), c = 19.998(2), β = 104.720(4)o, C54H48N4O11Zn, Mr = 994.33, V = 4690.2(9)3, Dc = 1.408 g/cm3, Z = 4, F(000) = 2072, μ(MoKα) = 0.59 mm-1, R = 0.0736 and wR = 0.2029. The crystal structure shows that the zinc ions are coordinated with two oxygen atoms from two HL molecules and four nitrogen atoms from two phen molecules, forming distorted octahedral coordination geometry. The fluorescent and thermal stability properties of the complex are studied. The result shows that it has one fluorescent emission band at around 412 nm. In addition, the complex is stable under 210 ℃.     

Hydrothermal Synthesis,Crystal Structure and Properties of a 1D Chain Copper(Ⅱ) Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)

A new 1D copper(Ⅱ) polymer [Cu(Hpt)(3,5-DMBA)]n has been hydrothermally synthesized with copper acetate,3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3,5-dimethylbenzoic acid(3,5-DMBA). It crystallizes in triclinic space group P1,with a = 8.1974(6),b = 8.3280(6),c = 12.5021(9) ?,α = 84.3320(10),β = 71.8870(10),γ= 65.4560(10)o,V = 737.44(9) ?~3,Dc = 1.612 g/cm3,Z = 2,F(000) = 366,GOOF = 1.035,R = 0.0298 and w R = 0.0855. The crystal structure is a one-dimensional(1-D) chain in which the Cu(Ⅱ) is five-coordinated with square pyramidal geometry. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ12-η:η0-3,5-dimethylbenzoic acid anions and two 3-(pyridin-2-yl)-1,2,4-triazole molecules. The coordination environment of Cu(Ⅱ) ion is CuO+2N_3. The luminescence and thermal properties of the complex were investigated.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Zn（phen）（m-CBA）2（H2O）

A novel complex Zn(phen)(m-CBA)2(H2O) with m-chlorobenzoic acid (m-CBA), 1,10-phenanthroline (phen) and zinc chloride has been hydrothermally synthesized and characterized. Crystal data for this complex: triclinic, space group P1, a = 0.8361(5), b = 1.2455(7), c = 1.3107(7) nm, α = 115.637(8), β = 91.014(9), γ = 104.857(8)o, V = 1.1763(11) nm3, Dc = 1.623 g/cm3, Z = 2, F(000) = 584, GOOF = 1.078, the final R = 0.0453 and wR = 0.1192. Structure analysis shows that the zinc ion coordinates with two nitrogen atoms of one 1,10-phenanthroline molecule, three oxygen atoms from two m-chlorobenzoic acid molecules and one water molecule, giving a distorted square-pyramidal coordination geometry. The cyclic voltametric behavior of the complex was also investigated.     

Synthesis,Crystal Structure and Properties of the Cobalt(Ⅱ) Complex of Methyl-5-norbornene-2,3-dicarboxylic Acid

A new cobalt complex Co(C10H8N2)(H2O)3[C9H11O2(COO)] with methy-5-norbornene-2,3-dicarboxylic anhydride acid(MNA) and 2,2'-bipyridine as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in monoclinic, space group P21/c with a = 13.0430(13), b = 21.014(2), c = 7.5151(7) ?, β = 102.319(2)o, V = 2012.4(3) ?3, Dc = 1.529 g/cm3, Z = 4, F(000) = 964, GOOF = 1.051, the final R = 0.0457 and wR = 0.0974. The crystal structure shows that the cobalt ion is coordinated with four oxygen atoms from one MNA molecule and three water molecules together with two nitrogen atoms from the 2,2'-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties have studied in this paper.     

Synthesis, Crystal Structure and Properties of a Dinuclear Cobalt（II） Complex [Co2（a-furacrylato）4（Phen）2（H2O）]·C2H5OH

A dinuclear cobalt(Ⅱ) complex [Co2(α-furacrylato)4(Phen)2(H2O)]·C2H5OH has been synthesized with α-furacrylic acid and 1,10-phenanthroline as the ligands, and its crystal structure was determined. The crystal is of monoclinic system, space group C2/c with a=1.07388(8), b=2.4300(2), c=1.86708(14)nm, β=104.3830(10)o, V=4.719.4(7) nm3 , Dc=1.503 g/cm3 , Z=2, F(000)=2196, GOOF=1.053, the final R=0.0343 and wR=0.0883. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked by the bridging coordination of two α-furacrylic acid anions and one water molecule, and their end positions are respectively coordinated with two 1,10-phenanthroline molecules and two α-furacrylic acid anions, forming a dinuclear structure. Both cobalt(Ⅱ) ions adopt hexa-coordinated distorted octahedral geometry. The electrochemical and fluorescence properties of the title complex are also discussed.     

Synthesis and Crystal Structure of a Dinuclear Complex： Bis[aqua（phen）（4- aba）copper（Ⅱ）nitrate（4-abaH）dihydrate]

The title complex has been obtained by the reaction of copper nitrate tri-hydrate with 4-abaH (4-abaH=4-aminobenzonic acid) and phenanthroline in ethanol solution,and its structure was determined by X-ray crystallography with the following data: monoclinic,space group C2/c,Mr=1266.13,Cu2C52H54N10O20,a=25.884(5),b=10.205(2),c=20.849(4) ,β=106.34(3)°,Z=4,V=5284.7(18) 3,F(000)=2616,Dc=1.591 g/cm3,μ=0.896 mm-1,the final R=0.0441 and wR=0.1148 for 4200 observed reflections (I > 2σ(I)). In the molecule of the title complex,the asymmetric unit contains one half molecule. The Cu(Ⅱ) atom is five-coordinated by a terminal water molecule,a bidentate phenanthroline and two monodentate 4-aminobenzoate ligands forming a square pyramidal coordination environment. The two bridging 4-aminobenzoate ligands result in a dinuclear copper(Ⅱ) cluster with a short Cu–Cu distance (3.048 ) and a π-π stacking between the adjacent phenanthroline rings (2.96 ).     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Cu（α-Furacrylic acid）2（phen）

The title complex (C26H18CuN2O6,Mr=517.96) has been synthesized by the reac-tion of α-furanacrylic acid with 1,10-phenanthroline (phen) in the solvent mixture of water and methanol. Crystal data: monoclinic,space group C2/c with a =2.2927(4),b=1.01248(18),c=1.05061(18) nm,β=111.188(3)o,V=2.274(7) nm3,Dc=1.513 g/cm3,Z=4,F(000)=1060,μ= 1.007mm?1,R=0.0320 and wR=0.0781. The crystal structural analysis shows that the copper atom is coordinated with four oxygen atoms from two α-furacrylic acids and two nitrogen atoms from 1,10-phenanthroline,giving a distorted octahedral coordination geometry. The result of electroche-mical analysis shows that the electron transfer in the electrode reaction is quasi-reversible.     

Hydrothermal Synthesis, Structure and Thermal Stability of a Copper Coordination Polymer Bridged by Pimelic Acid

A novel one-dimensional chain copper（Ⅱ） coordination polymer { [Cu（2,2′-bipy）- （HPDA）]（HPDA）（H2O）}n has been hydrothermally synthesized using pimelic acid, 2,2′-bipyridine and copper perchlorate in the mixture of water and methanol. The crystal structure was determined as a monoclinic system, space group P21/c, with a= 1.01139（14）, b = 2.6898（4）, c = 1.02105（14）, β = 109.651（2）°, V = 2.6159（6） nm^3, Dc = 1.412 g/cm^3, Z = 2, F（000） = 1164, GOOF = 1.044, R = 0.0570 and wR = 0.1448. The copper ion is coordinated with two nitrogen atoms of one 2,2′- bipyridine molecule and three oxygen atoms from two heptane diacid molecules, forming a distorted square-pyramidal geometry. The result of TG analysis shows that the title complex is stable under 200.0 ℃.     

Solvothermal Synthesis,Crystal Structure and Electrochemical Property of Complex [Co(p-MBA)_2(2,2′-bipy)(H_2O)]·(H_2O)

One novel complex [Co(p-MBA)2(2,2′-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2′-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic,space group P1 with a=0.70479(14),b=1.1211(2),c=1.6718(3) nm,α=103.806(3),β=90.795(3),γ=104.207(3)o,V=1.2399(4) nm3,Mr=512.41,Dc=1.373 g/cm3,Z=2,F(000)=532,μ=0.733 mm-1,R= 0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2′-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported.     

Synthesis,Crystal Structure and Properties of the Cobalt（II） Complex of Methy-5-norbornene-2,3-dicarboxylic Acid

A new cobalt complex Co（C10H8N2）（H2O）3[C9H11O2（COO）] with methy-5-norbor- nene-2,3-dicarboxylic anhydride acid （MNA） and 2,2＇-bipyridine as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in monoclinic, space group P21/c with α = 13.0430（13）, b = 21.014（2）, c = 7.5151（7） ？, β = 102.319（2）o, V = 2012.4（3） A3, Dc = 1.529 g/cm3, Z = 4, F（000） = 964, GOOF = 1.051, the final R= 0.0457 and wR= 0.0974. The crystal structure shows that the cobalt ion is coordinated with four oxygen atoms from one MNA molecule and three water molecules together with two nitrogen atoms from the 2,2＇-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stabilityand electrochemical properties have studied in this paper.     

Hydrothermal Synthesis, Crystal Structure, Spectrum and Electrochemical Analysis of the Copper（Ⅱ） Coordination Polymer

The three-dimensional framework copper(Ⅱ) coordination polymer with basic copper carbonate and 3-(pyridin-2-yl)-1,2,4-triazole has been hydrothermally synthesized. It crystallizes in monoclinic space group P21/c, with a = 1.20860(3), b = 1.29581(2), c = 1.67863(3) nm, β = 116.0280(2)°, C21H12Cu3N12, Mr = 623.05, V = 2.36230(9) nm3, Dc = 1.752 g/cm3, Z = 4, F(000) = 1236, GOOF = 1.037, the final R = 0.0408 and wR = 0.1141. Every unit cell contains three copper atoms and three 3-(pyridin-2-yl)-1,2,4-triazole ligands. Every central Cu(Ⅱ) ion is coordinated by four nitrogen atoms of the 3-(pyridin-2-yl)-1,2,4-triazole ligands, forming a distorted tetrahedron. The title complex exhibits an intense photoluminescence at room temperature with the maximum emission at 392 nm. The cyclic voltametric behavior of the complex shows that the electron transfer in electrolysis reaction is irreversible.