A Benzimidazole-pyridine-2,3-dicarboxylic Acid Bridged Zinc(Ⅱ)Coordination Complex–crystal Structure,Quantum Chemistry and Luminescence

The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ)Complexes Containing Flexible Bis(benzimidazole)Ligands

Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.

Chemical fixation of carbon dioxide to cyclic carbonates catalyzed by zinc(Ⅱ) complex bearing 1,2-disubstituted benzimidazole ligand

A new zinc(II)complex of formula[ZnCl2(L1)2](1)[L1=2‐(2‐thienyl)‐1‐(2‐thienylmethyl)‐1Hbenzimidazole]was synthesized and fully characterized by nuclear magnetic resonance and infrared spectroscopy,elemental analysis,electrospray ionization high‐resolution mass spectrometry,and thermogravimetric analysis.The molecular structure was confirmed by single‐crystal X‐ray diffraction.Complex1consists of mononuclear tetrahedral zinc(II)units with a locked geometry resulting from weak intramolecular S···?and?–?interligand interactions.The benzimidazole ligand and its zinc(II)complex were readily obtained through a simple synthetic route.The catalytic activity of1was investigated in the coupling of carbon dioxide with epoxides to produce cyclic carbonates,and a series of parameters were evaluated.The complex efficiently catalyzed the transformation of various epoxides under solvent‐free conditions,with good conversions,turnover numbers,and turnover frequencies.

Trihydrated Complex of Tetrabenzimidazole Copper(Ⅱ) Sulfate

A Trihydrated complex of benzimidazole copper(Ⅱ) sulfate [(C 7H 6N 2) 4CuSO 4]·3H 2O 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 H 2O 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.

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu（C9H11N3）Cl2]2（C18H22Cl4Cu2N6）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic P1^- space group with a = 7.526（3）, b = 9.473（4）, c = 9.535（3）A, α = 117.214（10）, β = 108.251（9）, γ = 91.560（6）°, V = 562.3（4）A^3, Z = 1, Mr = 591.30, F（000） = 298, Dc = 1.746 g/cm^3, μ（MoKα） = 2.385 mm^-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones （Ⅰ〉 2σ（Ⅰ））. In the title complex, each copper（Ⅱ） atom is located at the center of a distorted trigonal bipyramid of five coordination atoms （two nitrogen and three chlorine atoms）. Two copper（Ⅱ） atoms were bridged by two chlorine anions （Cl（2） and Cl（2a）） to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity with the distance between two copper（Ⅱ） atoms of 3.398 （A）.

Synthesis and Crystal Structure of a Novel Dinuclear Copper(Ⅱ) Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper（Ⅱ） complex [CuL（NO3）]2·2MeOH was obtained by the coordination reaction of Cu（NO3）2·3H2O with ligand HL （HL=N-（methyl-2-benzimidazol- methylidene）-2-hydroxyaniline）. The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535（3）, b=10.009（3）, c=10.666（4） , α=104.303（4）, β=100.105（4）, γ=115.917（4）o, V=839.0（5） 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F（000）=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper（Ⅱ） complex units [CuL（NO3）]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper（Ⅱ） units.

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 ℃.

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.

Hydrothermal Synthesis, Crystal Structure and Fluorescence Properties of a Three-dimensional Triply-bridged Binuclear Zinc(Ⅱ) Complex [Zn_2(Mba)_3(Phen)_2EtOH)]·ClO_4

The novel complex [Zn2（Mba）3（Phen）2EtOH）]·ClO4 （Hrnba = methoxybenzoic acid, Phen = 1,10-phenanthroline, EtOH = ethanol） was synthesized by hydrothermal reactions, and its structure was determined by X-ray diffraction. The crystal belongs to the triclinic system, space group Pi with a = 1.15362（1）, b = 1.3655（3）, c = 1.61451（1） nm, α= 72.842（2）, β = 83.259（3）, y = 72.083（2）°, V = 2.3112（6） nm3, Z = 2,μ（MoKa） = 11.71 cm-1, F（000） = 1120, R = 0.0552 and wR = 0.1157 （I 〉 2σ（I））. The two centric zinc（H） ions in the complex locate in a distorted octahedral coordination geometry and a distorted trigonal bipyramid coordination geometry, respectively. Two bridging bidentate carboxyl groups and a μ2-O carboxyl group from three methoxybenzoic acids act as the bridge to link two Zn（Ⅱ） ions. The asymmetric units are connected by π-π packing interactions between aromatic rings to form a three-dimensional supramolecular network. The experimental results show a good fluorescence property for the complex.

Synthesis, Crystal Structure and Biological Properties of One Zinc(Ⅱ) Complex Based on 4-Acyl Pyrazolone Derivative

[Zn（L）（CH3OH）3]（H2L = N-（1-phenyl-3-methyl-4-propenylidene-5-pyrazolone）-salicylidene hydrazide） has been synthesized by the reaction of zinc nitrate and ligand H2 L. The complex crystallizes in orthorhombic system, space group Pbca with a = 5.888（15）, b = 14.564（14）, c = 22.20（2） , V = 5137（8） 3, Z = 8 and F（000） = 2184. The ligand serves as a negative bivalent tridentate chelating agent to coordinate with the central zinc（II） atom. DNA-binding was studied by UV-Vis spectral analysis and ethidium bromide（EB） displacement experiments. The results showed that the DNA-binding constant of the complex is 5.1×104 M–1. Antitumor activity of [Zn（L）（CH3OH）3] and the ligand have been investigated by MTT assay, which indicated that the complex has better cytotoxicity to Eca-109 and He La than free ligand.

Synthesis,Crystal Structure and Properties of a Zinc(Ⅱ) Complex Based on 5-(1H-Tetrazol-5-yl)isophthalic Acid Ligand

A novel polymeric zinc（II） complex {[Zn2（TIA）（H2O）3]·（NO3）}n（1, H3TIA = 5-（1H-tetrazol-5-yl）isophthalic acid） has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a = 10.4210（6）, b =23.3526（14）, c = 6.9214（4）A, V = 1684.37（17）A^3, Z = 4, C9H4N5O（10）Zn2, Mr = 472.91, Dc = 1.865g/cm^3, F（000） = 932, λ（MoK α） = 2.909 mm^-1, R = 0.0423 and wR = 0.1287. The complex has good thermal stability and excellent photoluminescent property.

基于4-羟基间苯二甲酸和含氮杂环配体的Zn(Ⅱ)配合物的合成、晶体结构与荧光性质研究

在水热法条件下,4-羟基间苯二甲酸(H 2HPHA)和锌离子分别与1,2二(吡啶-4-基)乙烯(dpee)及4,4′-联吡啶(4,4′-bpy)反应得到了2个三维的配位聚合物[Zn(HPHA)(dpee)·(DMA)2]n(配合物1)和[Zn(HPHA)2(4,4′-bpy)2·DMA]n(配合物2)。用X射线单晶衍射测定了配合物的晶体结构,结果显示:配合物1属于单斜晶系,C2空间群,每个不对称单元由一个锌离子,一个4-羟基间苯二甲酸配体及一个1,2-二(吡啶-4-基)乙烯组成;配合物2属于单斜晶系,P12/c1空间群,每个不对称单元由两个锌离子,两个4-羟基间苯二甲酸配体及两个4,4′-联吡啶配体组成。荧光光谱分析结果表明:配合物1的最强激发峰和发射峰在分别在251和397 nm,配合物2的最强激发峰和发射峰分别在415和513 nm。热重分析表明两个配合物在室温下稳定。

Synthesis and Characterization of a Trinuclear Zinc(Ⅱ) Complex with Schiff Base (1R,2R)-(-)-Diaminocyclohexane- N,N'-biscarboxyl-salicylidene)

A homochiral complex, Zn3（Hsalen）2（Py）4（H2O）2 （salen = （1R,2R）-（-）-diamino-cyclohexane-N,N＇-biscarboxyl-salicylidene） 1, has been synthesized by solvothermal procedure and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. It crystallizes in monoclinic space group P2 with a = 10.9439（7）, b = 10.1722（6）, c = 27.3450（17）, β = 97.5060（10）o, V = 3018.1（3） 3, Z = 2, Zn3（Hsalen）2（Py）4（H2O）2, Mr = 1363.33, Dc = 1.500 g/cm3, F（000） = 1408, μ = 1.257 mm-1, GOOF = 1.042, the final R = 0.0601 and wR = 0.1464 for 10322 observed reflections with I 2σ（I）. The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by strong hydrogen bonding interactions and the polymeric chains are further assembled into a 2D supramolecular network structure via C–H···π interactions between the cyclohexane and aromatic rings of the ligand of adjacent chains. Simultaneously, π···π stacking interactions play an important role in forming the 2D supramolecular framework.

Synthesis,Crystal Structure,Spectroscopic Characterization and Thermal Stability Properties of a Trinuclear Zinc(Ⅱ) Complex

A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C_(13)H_9N_2O)Cl]_2·(CH_3CN)_2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu（C13HgN2O）Cl]2.（CH3CN）2 （C30H24C12Cu2N6O2）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclirile system, space group P1, with a = 7.6677（14）, b = 9.2375（17）, c = 11.227（2） ]A, α = 81.338（3）,β = 88.173（4）, γ = 66.199（3）°, V = 718.9（2） ]A^3, Z = 1, Mr = 698.53, F（000） = 354, Dc = 1.613 g/cm^3, μ（MoKa） = 1.705 mm^-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones （I 〉 20（I））. In the title complex, each copper（H） atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms （one nitrogen atom, two oxygen anions, and one chlorine atom）. Two copper（Ⅱ） atoms are bridged by two oxygen anions （O（1） and O（la）） of two phenolates to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity, and the distance between two copper（Ⅱ） atoms is 3.0144（15） A.

Synthesis and Crystal Structure of a Zinc(II) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

The title zinc（Ⅱ） complex salt [Zn（H2O）6]（ClO4）2-（PNOS）4, where PNOS is derived from picolinaldehyde N-oxide with semicarbazone, has been prepared and structurally characterized by X-ray single-crystal analysis. It crystallizes in triclinic, space group PI with a = 7.529（3）, b = 10.206（4）, c = 14.678（6）A, a = 86.293（6）, β= 87.686（7）, γ= 81.382（6）°, C28H44Cl2N16O22Zn, Mr = 1093.06, V = 1112.3（8） ,A^3 Z = 1, Dc = 1.632 g/cm^3, S = 1.089, μ（MoKa） = 0.773 mm^-1, F（000） = 564, the final R = 0.0438 and wR = 0.1076 for 3888 independent reflections with Rint = 0.0224. The crystal structure possesses a [Zn（H2O）6]^2＋ cation, two ClO4^- anions and four PNOSs. In the crystal structure, Zn^2＋ cation is located at the symcenter and coordinated by six water molecules. In [Zn（H2O）6]^2＋, an elongate octahedral complex cation, the average Zn-O bond length is 2.087（2） A. There exist a lot of H bonds in the structure, linking the cation [Zn（H2O）6]^2＋, anion ClO4^- and PNOS to form a 3D network.

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc(II) Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc（Ⅱ） complexes, [Zn2L2Ch].2[ZnL（CH3OH）Cl2] 1 and [ZnL2（NO3）2] 2, were synthesized by reacting ZnX2.nH2O （X = Cl^-, NO3^-） and a Schiff base ligand 2-[（4-methylphenylimino）methyl]-6-methoxyphenol （C15HIsNO2, L） which was obtained by the condensation of o-vanillin （2-hydroxy-3-methoxybenzaldehyde） with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, IH-NMR spectra and thermogravimetrie analysis. The Schiff base ligand and its zinc（Ⅱ） complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.

A Novel Three-dimensional Triazole-based Zinc(Ⅱ) Coordination Polymer Controlled by the Spacers of Dicarboxylate Ligand with(4~2,6~2,8~2)(4,6~2,8~3) Topology

A novel mixed-ligand coordination polymer [Zn(BTA)(ip)0.5]n(1, HBTA = benzotriazole, H2 ip = isophthalic acid) has been synthesized under hydrothermal conditions, which was further characterized by X-ray diffraction, IR spectrum, elemental analysis and TG-DTA experiments. Complex 1 crystallizes in monoclinic system, space group Pnma with a = 8.9731(5), b = 22.0477(12), c = 10.0217(5) ?, V = 1982.66(18) ?3, Z = 8, C10 H6 ZnN3 O2, Mr = 265.55, Dc = 1.779 g/cm3, μ = 2.462 mm-1, F(000) = 1064, the final R = 0.0225 and wR = 0.0652 with I > 2σ(I). This complex is a 3 D framework with the(42,62,82)(4,62,83) topology. Furthermore, the thermal stability of complex 1 is observed to be dependent on the polymeric structure nature. Strong solid-state luminescence emissions suggest that complex 1 is a good candidate for light emission materials.

Synthesis, Crystal Structure and Kinetic Mechanism of Thermal Decomposition of a Zinc(II) Complex with N-Salicylidene-p-toluidine

The title complex, Zn（C24H13NO）2Cl21, has been synthesized by the reaction of zinc chloride with Schiff base ligand N-salicylidene-p-toluidine and its structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Cc with a = 14.896（3）, b = 12.506（2）, c = 15.352（3） A,β = 114.711 （4）°, V = 2598.0（8） A^3, C28H26ZnCl2N2O2, Mr = 558.80, Z = 4, Dc = 1 .429 g/cm^3,μ = 1.179 mm^-1, Flack parameter = 0.027（19）, F（000） = 1152, R = 0.0709 and wR = 0.1041 for 3117 observed reflections （Ⅰ 〉 2σ（Ⅰ））. In complex 1, the center Zn ion is four-coordinated by two O atoms from two Schiff base ligands and two Cl atoms in a distorted tetrahedral geometry. Additionally, the thermal decomposition of complex 1 as well as its kinetic mechanisms and equations is studied under the non-isothermal integral and differential methods in air by TG-DTG curves.