苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

镧系四元混合配体配合物[Ce(CH2ClCOO)2(NO3)(phen)(H2O)]2的晶体结构、芳环堆积效应和2D氢键网络

The quaternary complex, ［Ce(CH2ClCOO)2(NO3)(phen)(H2O)］2, was synthesized. Interestedly, the title compound is a dimer comparing with the 1D polymer ［La(CH2ClCOO)2(NO3)(phen)*(H2O)］n and powder compound ［Nd(CH2ClCOO)2(NO3)(phen)］. In the title compound there is a monodentate NO-3, which is a first example in the all synthesized quaternary mixed anion complexes, and the NO-3 extended the complex into a 2D network with water from other molecules by inter-molecular hydrogen bonds. The intermolecular hydrogen bonds lead to the weaker Ce—O(COO), Ce—O(NO3) and Ce—N bonds comparing with other quaternary mixed anion complexes of cerium. Also the stacking effect, which makes the compound more stable in the situation of weaker Ce—O and Ce—N bonds, was first found in the series compounds.     

Syntheses,Crystal Structures and Properties of Co（Ⅱ） and Cu（Ⅱ） Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co(O2N-Hbtb)(phen)(H2O)3]·2H2O}n 1 and {[Cu3(O2N-btb)2(bipy)2(H2O)4]·4H2O}n 2(O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2'-bipyridine),were prepared through hydrothermal reactions of Co(Ⅱ) or Cu(Ⅱ) salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.     

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.     

Unprecedented Pseudo Water Tapes Stabilized by a One-dimensional Cu（Ⅱ） Coordination Polymer

A new compound,[Cu(mal)(tmdpy)(H2O)]·4H2O(1,H2mal = malonic acid,tmdpy = 4,4'-trimethylenedipyridine) has been synthesized by the hydrothermal synthesis and structurally characterized by X-ray crystallography. It crystallizes in triclinic,space group P1 with a = 9.1662(6),b = 10.6266(7),c = 11.3056(7) ,α = 84.6390(10),β = 72.1030(10),γ = 73.0420(10) o,V = 1002.37(11) 3,C16H26CuN2O9,Mr = 453.93,Z = 2,Dc = 1.504 g/cm3,μ = 1.140 mm-1,F(000) = 474,R = 0.0375 and wR = 0.0975 for 3187 observed reflections(I > 2σ(I)) . In the structure of 1,the tmdpy ligands link the [Cu(mal)(H2O) ] units into an infinite chain,and the water molecules and carboxylate oxygen donors(O(2) and O(4)) from the mal ligands cooperatively built an interesting hydrogen bonding network with unprecedented pseudo water tape substructures.     

Synthesis,Structure and Luminescent Properties of [Zn(btzb)2Cl2]·2H2O[btzb=1,2-Bis(5-tetrazolyl)benzene]

The title compound[Zn(btzb)2Cl2]·2H2O(1·2H2O,btzb=1,2-bis(5-tetrazolyl)benzene)was synthesized in situ by the[2 3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions.1·2H2O crystallizes in the monoclinic system,space group P21/c with a=9.0119(18),b=7.5566(15),c=18.076(5)(A),β=114.67(2)°,V=1118.6(4)(A)3,Z=2,Dc=1.784 g/cm3 T=223(2)K,C16H16N16O2Cl2Zn,Mr=600.74,F(000)=608,μ(MoKα)=1.393 mm-1,S=1.081,R=0.0306 and wR=0.0669 for 1896 observed reflections with Ⅰ ＞2σ(Ⅰ).The Zn2 ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms,forming a distorted octahedral coordination geometry.A number of intermolecular hydrogen bonding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure.The luminescent property of 1·2H2O was also investigated.     

Structures of 1-（3,4-Dihydroxyphenyl）-2-（3,4-dimethoxyphenyl） ethanone and Its Hydrate Complex

The title compounds, C16H16O5 (I) and C16H16O5·H2O (II), were structurally characterized by single-crystal X-ray diffraction. Compound I crystallizes in monoclinic space group P21/c with a = 10.5574(10), b = 8.3576(9), c = 16.5528(16) , β = 91.762(3)°, Z = 4, R = 0.0524 and wR = 0.1084. The molecules are jointed into a chain by intermolecular O-H···O and C-H···O hydrogen bonds, which form layers parallel to (001). The chains run along the [110] and [110] directions alternatively layer by layer, and are assembled into a network by intermolecular O-H···O (carboxyl) hydrogen bonds. On the other hand, the hydrate complex (II) crystallizes in the triclinic space group P1 with a = 5.1451(2), b = 10.4583(4), c = 14.8267(5) , α = 70.900(2), β = 82.478(2), γ = 81.359(2)°, Z = 2, R = 0.0393 and wR = 0.0983. The molecules are linked into infinite two-dimensional ribbons by O-H···O (carbonyl) and solvent-bridged O-H···O hydrogen bonds.     

Syntheses, Crystal Structures and Electrochemical Properties of Two Molybdophosphates

Two molybdophosphate compounds,[Ni(bim)3]2[H2P2Mo5O23]·2H2O 1 and [Zn(bpy)2]2[Zn(bpy)(H2O)]2Zn[Mo6O12(OH)3(HPO4)4]2·9H2O 2 (bim = 2,2'-biimidazole,bpy = 2,2'-dipyridyl),have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis,TG,and IR. The single-crystal X-ray analysis exhibits that 1 consists of one [H2P2Mo5O23]4-,two [Ni(bim)3]2+ cations and two lattice water molecules,while 2 is constructed from one sandwich-type [ZnP4Mo6] anion modified by four Zn-bpy complexes and nine lattice water molecules. The electrochemical behaviors of compounds 1 and 2 have been studied in detail based on solid bulk modified carbon paste electrodes of compound (CPEs).     

Crystal Structure and Luminescence of a New Zn(Ⅱ) Complex [Zn(L)(IPP)(H_2O)]·2H_2O Based on Nicotinate Derivative and 1,10-Phenanthroline Derivative

A new Zn(Ⅱ) complex, [Zn(L)(IPP)(H2O)]·2H2O(1, H2 L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and IPP = 2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol), was synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 8.5023(17), b = 9.945(2), c = 15.573(3) ?, α = 95.87(3), β = 102.56(3), γ = 100.73(3)o, V = 1248.7(4) ?3, Z = 2, C27H22N5O9 Zn, Mr = 625.87, Dc = 1.665 g/cm3, F(000) = 642, μ(Mo Ka) = 1.053 mm-1, R = 0.0474 and w R = 0.1352. In 1, one L2-, one IPP and one water molecule coordinate to the same Zn(II) atom to give a discrete complex with two lattice water molecules. Adjacent [Zn(L)(IPP)(H2O)]·2H2O molecules interact through π-π stacking between two IPP ligands to form a supramolecular chain. The N–H···O and O–H···N hydrogen bonds further stabilize the supramolecular chain structure of 1. The solid state luminescent property of 1 was also studied.     

Synthesis and Crystal Structure of Diaquabis{2,4- dibromo-6-[（2-ethylaminoethylimino）methyl]- phenolato}nickel（II） Dinitrate Diacetonitrile

The title mononuclear Schiff base nickel(Ⅱ) complex [Ni(C11H14Br2N2O)2(H2O)2]·2NO3·2C2H3N was prepared and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 15.534(2), b = 7.647(1), c = 16.435(2) (A), β = 103.252(2)o, V = 1900.3(4) (A)3, Z = 2, Dc = 1.750 g/cm3, Mr = 1000.99, λ(MoKα) = 0.71073 (A), μ = 4.776 mm-1, F(000) = 996, the final R = 0.0368 and wR = 0.0724. A total of 3988 unique reflections were collected, of which 2764 with I＞2σ(I) were observed. The complex consists of a mononuclear [Ni(C11H14Br2N2O)2(H2O)2]2 cation, two nitrate anions and two acetonitrile molecules. The Ni atom, lying on the inversion centre, is six- coordinated by two Schiff bases and two water molecules to assume an octahedral coordination geometry. The molecules in the crystal are linked through intermolecular hydrogen bonds of N-H…O, N-H…Br, O-H…O, O-H…N and C-H…O to form layers.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Novel Water Cluster [Mn(phen)_2·H_2O·Cl]·p-FBA·3H_2O

A novel water cluster [Mn(phen)2·H2O·Cl]·p-FBA·3H2O (p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768(1),b = 11.5960(1),c = 12.9916(2) ,α = 101.816(2),β = 95.397(2),γ = 103.052(2)o,V = 1502.8(3) 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese(Ⅱ ) ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a (H2O)4 water cluster. This water pattern forms a cross-linked discrete ring. The steady (H2O)4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional (1D) structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.     

Synthesis and Crystal Structure of 3,3＇-Bis（2-benzimidazolyl）-2,2＇-dipyridine with Hydrated Zinc（Ⅱ） Perchlorate

The reaction of Zn(ClO4)2·6H2O with 3,3'-bis(2-benzimidazolyl)-2,2'-dipyridine (L) gave a mononuclear zinc(II) complex: [ZnL2](ClO4)2·2DMF·4H2O, which was structurally characterized by EA, IR, UV, 1H NMR, fluorescence spectrum and single-crystal X-ray diffraction. The crystal (C54H54Cl2N14O14Zn, Mr = 1259.38) belongs to the monoclinic system, space group C2/c with a = 20.874(2), b = 14.9953(16), c = 20.462(3) , β = 101.553(2)°, V = 6274.8(13) 3, Z = 4, Dc = 1.333 g/cm3, F (000) = 2608, μ(MoKα) = 0.548 mm–1, R = 0.0682 and wR = 0.1931 for 4984 observed reflections with I > 2σ(I). The Zn(II) is four-coordinated in a slightly distorted tetrahedral geometry through four N atoms from four benzimidazole units of two ligands. In the crystal lattice, the [ZnL2]2+ cations are linked to each other by extensive intermolecular hydrogen bonds between nitrogen atoms of benzimidazole rings, water and DMF molecules.     

Synthesis and Crystal Structure of One New Coordination Polymer： [Ni（qptc）0.5（bpp）（ H2O）]n

Solvothermal reaction of aromatic terphenyl-2,5,2?,5?-tetracarboxylic acid (H4qptc) ligand and the transitional metal cation of NiII in the presence of 1,3-bi(4-pyri- dyl)propane (bpp) affords one new coordination polymer, [Ni(qptc)0.5(bpp)(H2O)]n (1). The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, TGA, and magnetism. The qptc4- acts as a H-shaped ligand linking the NiII centers together to form a 2D polymeric [Ni(qptc)0.5]n layer consisting of alternately arranged left- and right-handed helical chains. Each 2D polymeric [Ni(qptc)0.5]n layer is further linked through the bridging bpp ligands, thus resulting in a unique (3,4)- connected network with the (62.8)(62. 84) topology. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 16.088(5), b = 14.913(5), c = 18.849(6) ?, β = 100.982(4), V = 4439(2) ?3, Z = 8, C24H21N2NiO5, Mr = 476.14, Dc = 1.425 g/cm3, F(000) = 1976 and μ(MoKα) = 0.912 mm-1. The final R = 0.0584 and wR = 0.1131 for 3894 observed reflections with I > 2σ(I) and R = 0.1224 and wR = 0.1279 for all data.     

A self-assembled (H2O)20(CH3OH)4 binary cluster containing a grail-shaped hexadecameric water cluster trapped in the cavity of a metal-ligand hybrid

A discrete centrosymmetric(H2O)20(CH3OH)4 binary cluster was confined in the cavity of a metal-ligand hybrid [Ag4(bpda)2(bpp)4·14H2O·2CH3OH] n(1)(where bpp = 1,3-bis(4-pyridyl)propane and H 2 bpda = 2,2’-biphenyldicarboxylic acid).The novel mixed water-methanol cluster consists of one grail-shaped hexadecameric cluster,four dangling water and four hanging methanol molecules.The(H 2 O) 16 cluster is composed of two pairs of edge-sharing(H2O) 5 rings attached to one(H2O) 4 core with twenty hydrogen bonds.Alternatively,the(H2O) 16 cluster is structurally similar to a complicated hydrocarbon generated by undergoing [2+2] cycloaddition of 1,2,3,4,5,6-hexahydropentalene,which reveals the resemblance between water clusters and organic compounds.     

Synthesis and Crystal Structure of Diaquabis{2,4-dibromo-6-[(2-ethylaminoethylimino)methyl]-phenolato}nickel(Ⅱ) Dinitrate Diacetonitrile

The title mononuclear Schiff base nickel(Ⅱ) complex [Ni(C11H14Br2N2O)2(H2O)2]· 2NO3·2C2H3N was prepared and characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group P21/n with a=15.534(2),b=7.647(1),c=16.435(2),β=103.252(2)o,V=1900.3(4)3,Z=2,Dc=1.750 g/cm3,Mr=1000.99,λ(MoKα)=0.71073,μ=4.776 mm-1,F(000)=996,the final R=0.0368 and wR=0.0724. A total of 3988 unique reflections were collected,of which 2764 with I > 2σ(I) were observed. The complex consists of a mononuclear [Ni(C11H14Br2N2O)2(H2O)2]2+ cation,two nitrate anions and two acetonitrile molecules. The Ni atom,lying on the inversion centre,is six-coordinated by two Schiff bases and two water molecules to assume an octahedral coordination geometry. The molecules in the crystal are linked through intermolecular hydrogen bonds of N–H…O,N–H…Br,O–H…O,O–H…N and C–H…O to form layers.     

Influence of Different Organic Carboxylate Anions on the Crystal Structure of Silver(Ⅰ)Coordination Polymers

The reaction of AgNO3 , 4,4′-bipyridine (bpy) and 2,2′-bipyridine-3,3′-dicarboxylic acid (H2bpdc)/2,2′-biquinoline-4,4′-dicarboxylic acid (H2bqdc)/1,3-benzenedicarboxylic acid (H2bdc) gave rise to block-like crystals of [Ag4(bpy)2(bpdc)2]·13H2O(1), [Ag2(bpy)(bqdc)(H2O)]·4.5H2O(2) and [Ag2(bpy)2(H2O)2](bdc)·3H2O(3) by slow evaporation. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions (bpdc2- , bqdc2- and bdc2- ) and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complex layers, and the abundant Ag···Ag, Ag···N and π-π stacking interactions further strengthen the 3D frameworks. The lattice water molecules are situated among the framework of crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of organic anions in the crystal packing. Additionally, the thermal properties of 1, 2 and 3 were also discussed in detail.     

1D Lanthanide Coordination Polymers Based on 3-（Pyridin-4,yl）benzoic Acid： Syntheses, Structures and Luminescent Properties

Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(H2O)2· H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoclinic system, space group P1. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.     

Synthesis and Crystal Structure of [Mn（DPMT）2Cl2（H2O）2]

The title compound [Mn(DPMT)2Cl2(H2O)2] (DPMT = 1-[[2-(2,4-dichlorophenyl)- 1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) was synthesized by the reaction of MnCl2·4H2O and DPMT in ethanol solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 23.913(4), b = 7.8883(13), c = 8.6291(14) , β = 95.816(3)o, V = 1619.4(5) 3, Z = 2, C24H26Cl6MnN6O6, Mr = 762.15, Dc = 1.563 g/cm3, μ = 0.950 mm-1, S = 1.045, F(000) = 774, R = 0.0462 and wR = 0.0981. The molecular structure is a centrosymmetric conformation, and two ligands are symmetrically located on both sides of the Mn atom. The manganese atom is surrounded by two nitrogen atoms from ligands, two chlorine atoms and two oxygen atoms from water molecules to form a slightly distorted octahedral geometry.     

Three New Polyoxometalates Derivatives Decorated by Phenanthroline and Transition-metal Cations(M=Zn~ⅡI,Co~Ⅱ , Ni~Ⅱ)

Three new Keggin polyoxometalates, [Zn(phen) 3 ] 2 [SiW 12 O 40 ]·5H 2 O(1), [Co(phen) 3 ] 2 [SiW 12 O 40 ](2) and [Ni(phen) 3 ] 2 [SiW 12 O 40 ]·2H 2 O(3)(phen=1,10′-phenanthroline) have been hydrothermally synthesized and characterized by elemental analysis, IR, crystal X-ray diffraction, thermogravimetric analyses(TGA) and fluorescence techniques. Complex 1, crystallized in the triclinic space group P1, consists of one [SiW 12 O 40 ] 4– anion, two discrete [Zn(phen) 3 ] 2+ cations and five crystal water molecules. Complexes 2 and 3 have the similar configuration to complex 1, but they crystallized in the monoclinic space group C2/c. Variable-temperature magnetic susceptibilities of complexess 2 and 3 reveal antiferromagnetism and ferromagnetism, respectively.     

Synthesis, Crystal Structure, Fluorescence Property and Antibacterial Activity of Two Unprecedented One-dimensional Chain Metal organic Coordination Polymers： Zn（H-SSA）（Phen）（H20）2 and Cu（H-SSA） （Phen） （H20）2

The reaction of 5-sulfosalicylic acid(H3-SSA) with o-phenanthroline(Phen),NaOH,and Mcl2(M=Zn,Cu) affords Zn(H-SSA)(Phen)(H2O)2(1) and Cu(H-SSA)(Phen)(H2O)2 (2),respectively ,compounds 1 and 2 are characterized by elemental analysis,IR,fluorescence spectra and single crystal Xray diffraction analysis.The X-ray diffraction analyses reveal that compounds 1 and 2 are isostructure.The 5-sulfosalicylic acid ligand loses two protons at the sulfo-group and carboxylic group during the reaction.The Zn(II) and Cu(II)ions are sixcoordinated and adopt distorted octahedral geometry,which are surrounded by two N atoms from Phen,two O atoms from two water molecules,one O atom from-SO3 group and one oxygen from carboxylic group of the other H-SSA.Compounds 1 and 2 have unprecedented one-dimensional linear chain formed by a repeating mononuclear structureal unit.which is bridged by H-SSA.The fluorescence intensity of 1 and 2 is stronger than that of Phen and H3-SSA at 400nm.The lowest excited single states of these complexes are assigned as mainly Phen localized 1(π π),The antibacterial activity test shows that compounds 1 and 2 strongly inhibit the growth of Streptococcus haemolyticus,Straphylococcus aureus and Escherichia coli.