Hydrothermal Synthesis and Crystal Structure of a Zinc(Ⅱ) Polymer with a Two-dimensional Layer Structure: [Zn(pzdc)(phen)] n·nH_2O

A metal-organic coordination compound formulated as [Zn(pzdc)(phen)] n·nH_2O 1 (H_2pzdc=pyrazine-2,3-dicarboxylic acid,phen=1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system,space group P2_(1/n) with α=11.607(2),b=11.719(2),c=13.140(3)(A),β=110.707(3)°,V=1671.9(6)(A)~3,C_(18)H_(12)ZnN_4O_5,Mr=429.69,D_c=1.707 g/cm~3,μ(MoKα)=1.511 mm~(-1),F(000)=872,Z=4,the final R=0.0356 and wR=0.0853 for 2713 observed reflections (Ⅰ> 2σ(Ⅰ). It exhibits an interesting two-dimensional layer structure and shows yellow photoluminescent property at room temperature.     

Temperature-dependent Syntheses of Two Manganese(Ⅱ) Coordination Compounds Based on an Ether-bridged Tetracarbolylic Acid

0D dinuclear manganese(Ⅱ) coordination compound and 1 D chain manganese(Ⅱ) coordination polymer, namely [Mn_2(μ-L)(phen)4]·4 H_2 O(1) and {[Mn_2(μ5-L)(phen)_2]·H_2O}n(2), have been constructed hydrothermally using H4 L(H4 L = 2,3,3',4'-diphenyl ether tetracarboxylic acid), phen(phen = 1,10-phenanthroline), and manganese chloride at 120 and 160℃, respectively. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or P2_1/c. Compound 1 discloses a discrete dimeric structure, which is assembled into a 3 D supramolecular framework through O–H···O hydrogen bond. Compound 2 has a chain structure. Structural differences between compounds 1 and 2 are attributed to the different reaction temperature. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.     

A Novel 3-D Zn(Ⅱ) Coordination Polymer for Inhibiting the Human Osteosarcoma Cells Growth

A new three-dimensional Zn(II) coordination polymer, namely [Zn_4(bpydb)_3(tz)2(H_2O)_2]n(1), has been synthesized by the self-assembly reactions of Zn(NO_3)_2·6H_2O, bpydb H_2, Htz and DMF. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional framework structure and is the first example of Zn-containing coordination polymers based on two kinds of ligands bpydb H_2 and Htz. It crystallizes in triclinic, space group P1 with a = 14.9953(12), b = 17.5335(17), c = 20.2381(11) ?, α = 115.225(7), β = 92.329(5), γ = 105.606(8)o, V = 4561.9(7) ?3, Z = 2, F(000) = 1644, Dc = 1.177 Mg/m3, Mr = 1616.76 and μ = 1.098 mm-1. The antitumor activities of compound 1 and its corresponding organic ligands(bpydb H_2 and Htz) were investigated for inhibiting human osteosarcoma cells(MG-63 and U-2 OS) growth by MTT assay. It was found that compared with the two ligands, compound 1 exerted rather potent activities against all of these cell lines.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Symmetric Multicarboxylate Ligand

A novel coordination polymer, namely [Zn_2(CAPA)(DMA)(H_2O)]_(2n)·n(H_2O)(1,H_4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585(5), b = 18.9733(10), c = 20.2044(14) ?, β = 101.144(7)o, V = 3030.9(3) ?~3, C_(56)H_(54)Zn_4N_4O_(21), M_r = 1378.58, Z = 2). The compound forms a three-dimensional(3D) supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.     

Hydrothermal Synthesis and Crystal Structure of a Zinc(Ⅱ)Coordination Polymer Assembled by Dpphen and H_2btec/btec

<正>A new metal-organic coordination polymer[Zn_2(dpphen)_2(H_2btec)(btec)_(0.5)]_n (dpphen=4,7-diphenyl-1,10-phenanthroline,H_4btec=1,2,4,5-benzenetetracarboxylic acid)1 was obtained via hydrothermal synthesis and characterized by elemental analysis,TG,IR spectrum and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic system,space group P2_l/n with a=16.2996(14),b=14.3332(12),c=25.247(2)(?),β=103.4050(10)°,V=5737.7(9)(?)~3, C_(63)H_(37)N_4O_(12)Zn_2,M_r=1172.71,D_c=1.358 g/cm~3,μ(MoKα)=0.902 mm~(-1),F(000)= 2396,Z=4, the final R=0.0684 and wR=0.1281 for 3728 observed reflections(I2σ(I)).It exhibits a two-dimensional network structure constructed by mixed ligands of dpphen and H_2btec/btec.     

THE STUDY OF SPECTRA AND X-RAY CRYSTAL STRUCTURE OF A NOVEL BIONICS INSECTICIDE——(CH_3)_2NHCH(CH_2S_2O_3)_2Na·H_2O

IR and NMR spectra of novel bionics insecticide—C_5NS_4O_6H_(12)Na·H_2O have been studied. The molecular and crystal structures of the compound also have been determined. The compound crystallizes in the monoclinic space group C_(2h)~5, - P2_1/n with α= 8.0972. (9) , b =16.262(4), c = 10.370(3), β= 94.26(2)° and z = 4.The result shows that N atom in this compound captures a proton to form HN~ group, Na~ is in statistical disorder. Therefore, the structural formula of tho compound is (CH_3)_2HN~ —CH(CH_2S_2O_3~-)_2·1/2 (Na~ )_2·H_2O.     

Hydrothermal Synthesis and Crystal Structure of a Cd~(2+) Supramolecular Coordination Complex{[Cd_2(HCAM)_2(H_2O)_4]·3.5H_2O}_n with a 3D Metal-organic Open Framework

<正>A three-dimensional coordination polymer {[Cd_2(HCAM)_2(H_2O)_4]·3.5H_2O}_n was synthesized by the hydrothermal reaction of H_3CAM(H_3CAM=4-hydroxypyridine-2,6-dicerboxylic acid)and Cd(NO_3)_2·4H_2O.The structure was characterized by elemental analysis,thermal gravimetric analysis,infrared spectroscopy and single-crystal X-ray diffraction.It crystallizes in triclinic,space group P_1~-with a= 9.4389(19),b=11.009(2),c=11.192(2)(?),α=87.87(3),β= 74.63(3),γ=81.22(3)°,V=1108.2(4)(?)~3,Z=2,D_c=2.164g/cm~3,μ=2.011 mm~(-1),F(000)=710,R =0.0419 and wR=0.1170.X-ray analysis reveals that the title compound adopts a one-dimensional staircase structure by carboxyl of H_3CAM and water molecules,and it is further linked by hydrogen bonds to form a 3-D metal-organic open framework.The thermal gravimetric analysis displays that the framework exists stably below 300℃.     

Non-Isothermal Decomposion Kinetics of Supermolecule Compound [Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]_2·phen·4H_2O

Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C_(10)H_(10)N_2O_4,H_3L) and 1,10-phenan-throline (C_(12)H_8N_2,phen) has been prepared.A yellow prismatic crystal of the compound was obtained,and themolecule crystallized in the triclinic space group P-1.There are two 9-coordinated complex molecules in everystructure unit,where every Eu atom is coordinated by three water molecules and two tridentate C_(10)H_(10)N_2O_4 ligands,forming two stable pentacycles.The coordination polyhedron around Eu~(3+) was described as a single cap squareantiprism.In the crystal cell,there are one free 1,10-phenanthroline and four water molecules.The thermaldecomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry.The Kissinger'smethod and Ozawa's method were used to calculate the activation energy value of the first-step decomposition.Thestages of the decompositions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were ana-lyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equationswere investigated by comparing the kinetic parameters.     

Ionothermal Synthesis,Structure and Luminescent Properties of a New 2-D Bismuth(Ⅲ) Coordination Polymer with(6,5)-Connected Topological Sheet

A new 2-D Bi~(3+) coordination polymer {Bi_4(μ_3-O)_2(μ_4-O)_2(C_7H_3NO_4)_2}_n(1,C_7H_3NO_4 = pyridine-2,6-dicarboxylate) containing(6,5)-connected topological sheet with the Schl?fli symbol of(4~4·6~3·8~4·12~4)(4~5·6~4·8) has been synthesized by an ionothermal method using the ionic liquid 1-ethyl-3-methylimidazolium bromide([Emim]Br) as solvent,and characterized by C,H and N elemental analysis,energy-dispersive X-ray spectroscopy(EDS),infrared spectrum(IR spectrum) and single-crystal X-ray diffraction.The results indicate that 1 belongs to the monoclinic system,space group P2_1/n with a = 13.766(7),b = 4.142(2),c = 16.439(8) ?,β = 99.099(9)°,Z = 2,V = 925.6(8) ?~3,Dc = 4.414 g·cm~(-3),F(000) = 1064,μ = 37.985 mm-1,the final R = 0.0326,wR = 0.0727 and S = 1.022.The molecular structural units [Bi_4(μ_3-O)_2(μ_4-O)_2(C_7H_3NO_4)_2] are connected to each other via bridging O atoms,extending into an interesting 2-D layered structure.These resulting layers are further assembled by weak C–H···O hydrogen bonds into a 3-D supramolecular architecture.Moreover,its thermal stability and the luminescent properties have been also studied.     

Synthesis,Crystal Structure and Luminescence Study of a New Two-dimensional Mn(Ⅱ) Coordination Polymer

The coordination polymer [Mn_2(cipt)_2(aic)_2]_n(cipt = 2-(3-chlorophenyl)-1Himidazo[4,5-f][1,10]phenanthroline, aic = 5-amino-isophthalic acid) has been obtained from hydrothermal reaction and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1, with a = 11.523(3), b = 12.162(3), c = 18.706(5) ?, β = 81.789(5)o, V = 2455.2(1) ?3, C_(54)H_(32)Cl_2Mn_2N_(10)O_8, Mr = 1129.68, Z = 2, Dc = 1.528 g/cm3, μ = 0.692 mm-1, F(000) = 1148, R = 0.064 and wR = 0.145 for 9571 observed reflections(I 2σ(I)). In this polymer, the Mn(Ⅱ) atoms adopt different coordination modes. The Mn(1) atom is five-coordinated, forming a distorted tetragonal pyramidal geometry. Mn(2) atom is six-coordinated to get a distorted octahedral geometry, which is different from the Mn(1) atom. Each Mn(Ⅱ) atom is linked by aic ligands with neighboring Mn(Ⅱ) atoms, forming an infinite one-dimensional(1D) double-chain structure. The existence of N–H···O hydrogen bonding interactions leads the 1D chains to generate a 2D structure. Luminescent properties for the ligand cipt and compound 1 have also been discussed in detail.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF CIS-BIS(1,10-PHENANTHROLINE)GLYCINECOBALT(Ⅲ)

A new coordination compound of cis-bis(1,10-phenanthroline)glycinecobalt(Ⅲ)chloridate tetrahydrate,cis-[Co(phen)_2gly]Cl_2.4H_2O,has been prepared by glycinereacted with cis-[Co(phen)_2Cl_2]Cl,then isolated by SP-Sephadex C-25 H~+ form column.The crystal and molecular structure of the new compound has been determined by RIGAKUAFC5R four circle diffractometer,5032 independent reflections were collected ofwhich 3781 observable reflections were used for structure refinement.The crystal ismonoclinic,space group C2/c,with a=35.13(1),b=9.637(3),c=17.485(6),β=115.08(Z)~,V=5362(3),Z=8.The structure was refined by full matrix least-squaresprocedure to a final R=0.041 and R_=0.060.The molecular formula was CoC_(28)H_(28)N_5O_8Cl_2.with molecular weight M_r=636.38,D_c=1.58g/cm~3,μ=8.88cm~(-1)and F_((000))=2624.     

Synthesis,Crystal Structure and Properties of a 1D Heteronuclear Cobalt-sodium Polymer with Bridging Ligand 2-(2-Hydroxy-3-methoxybenzylidene) Hydrazinecarbothioamide

A new cobalt-sodium coordination polymer [CoNa(C_9H_9N_3O_2S)_2·H_2O]_2·C_2H_3N·H_2O(1) has been synthesized with cobalt chloride,2-(2-hydroxy-3-methoxybenzylidene)hydrazinecarbothio amide(L) and sodium hydroxide.It crystallizes in the triclinic space group P1,with a = 9.972(4),b = 10.923(4),c = 13.489(5) ?,α = 108.005(10),β = 92.728(10),γ = 93.16(1)o,V = 1392.0(9) ?~3,Mr = 1151.95,Dc = 1.374 g/cm~3,Z = 2,F(000) = 592,the final GOOF = 1.126,R = 0.1091 and wR = 0.2412.Each unit molecule consists of two cobalt ions and two sodium ions bridged by four 2-(2-hydroxy-3-methoxybenzylidene)hydrazinecarbothio amide anions.The coordination environment of Co ion is CoO_2N_2S_2,giving a distorted octahedral geometry and the Na(1) ion is NaO_4N,giving a distorted square pyramidal geometry.The results show that 1 shows one strong intense fluorescence emission wavelength of 429 nm with an excitation wavelength of 376 nm,and the electron transfer of 1 is irreversible in electrode reactions.     

A New Europium Coordination Compound Supported by 4,6-Dibenzoylisophthalic Acid Ligands

A unique metal-organic framework(MOF) [Eu_2(L)_3(phen)_2]_n(1, H_2L = 4,6-dibenzoylisophthalic acid, phen = 1,10-phenanthroline) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray analysis, elemental analyses, powder X-ray diffraction, TGA measurement as well as IR spectra. The crystal is of triclinic system, space group P1, C_(90)H_(52)Eu_2N_4O_(18), M_r = 1781.32, a = 9.8697(4), b = 16.7466(6), c = 22.2556(10) ?, α = 87.113(3), β = 77.575(5), γ = 89.458(3)°, V = 3587.8(3) ?~3, Z = 2, D_c = 1.649 g/cm~3, F(000) = 1780, μ(MoKα) = 1.813 mm~(-1), Rint = 0.0181, R = 0.0260 and wR = 0.0592 for 14000 observed reflections with I 2σ(I). X-ray analysis shows that the title compound exhibits a 2D layer structure linked by L ligands with two coordination modes and two distinguished conformations, and further linked into a 3D supramolecular architecture through C–H···O weak interactions between hydrogen of phen phenyl ring and the carboxylate oxygen atom of adjacent sheets. In addition, the luminescence property of 1 was investigated.     

Synthesis,Crystal Structure and Photoluminescent Property of a Novel Dy~(3+) Coordination Compound Containing Rare(H_2O)_(22) Clusters

A novel Dy~(3+) coordination compound,(H_2pipz)(H_3O)[Dy(pydc)_3]·11H_2O(1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid),has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.     

Synthesis,Structure, and Properties of {[Mn(ADA)(Phen)]·(H_2O)_2}_n Constructed from Azobenzene-4,4?-dicarboxylic Acid and 1,10-Phenanthroline

One coordination polymer(CP) {[Mn(ADA)(Phen)](H_2O)_2}_n(1, H_2ADA = azobenzene-4,4?-dicarboxylic acid, Phen = 1,10-phenanthroline), has been synthesized via hydrothermal reactions. CP 1 was characterized by elemental analyses, IR spectra, thermal behaviors, and X-ray single-crystal diffraction. In CP 1, each ADA~(2-) ligand bridges two Mn~(2+) to give one-dimensional zigzag chains with the Mn···Mn separations of 17.6911 and 16.3976 ?, which generates a three-dimensional supramolecular structure by means of strong π···π interaction and hydrogen bonding. It crystallizes in triclinic, space group P1, with a = 7.6200(13), b = 9.1530(15), c = 18.262(2) ?, α = 88.467(3)o, β = 84.145(2)o, γ = 77.542(2)o, V = 1237.2(3) ?~3, Z = 2, C_(26)H_(20)MnN_4O_6, Mr = 539.40, Dc = 1.448 g/cm~3, F(000) = 554, S = 1.018, R = 0.0531 and w R = 0.1094. In addition, natural bond orbital analysis was performed by the B3 LYP/LANL2 DZ method of Gaussian 09 Program. The fluorescence, magnetic, and electrochemical properties of 1 have been investigated.     

A New Steady and Water-insoluble Polytungstate:Synthesis,Structure,Characterizations and Photocatalytic Properties

Polyoxometalate(POM)-based materials universally have some inherent flaws, including low recovery, metastability, solubility, etc., which may restrict their practical applications. Modifying the materials with organic-inorganic hybrid complexes is one of the most effective approaches to overcome these deficiencies. Under hydrothermal conditions, a new WellsDawson-type polytungstate modified Cd-complex, [Cd(phen)3]3[W_(18)O_(54)(PO_4)_2]·3H_2O(1, phen = 1,10-phenanthroline(C_(12)N_2H_8)), has been synthesized by selecting Cd~(2+) coordinated phen and employing stepwise self-assembly plans. The compound shows good stability and waterinsolubility under normal circumstances. Experiments demonstrate that compound 1 has ideal catalytic activity in the degradation reaction of rhodamine B(Rh B) under ultraviolet(UV)-light and oxidant H_2O_2 conditions. Detailed characterizations including X-ray single-crystal diffraction(XRD), Powder X-ray diffraction(PXRD), elemental analysis, energy-dispersive X-ray spectroscopy(EDS) analyses, Fourier transform infrared spectroscopy(FT-IR), UV-Vis-NIR diffuse reflection spectrum(DRS) and XPS spectrum are presented herein. The electrochemical(cyclic voltammetry(CV)) and photocatalytic properties of 1 have also been studied.     

A Dinuclear Dysprosium-2-quinolinecarboxylate-1,10-Phenanthroline Compound:Crystal Structure and Magnetism

A dinuclear dysprosium(III) compound,[Dy_2(μ_2-OH)_2(QLC)_4(1,10-phen)_2]·4H_2O(1)(QLC-= 2-quinolinecarboxylate and 1,10-phen = 1,10-phenanthroline),was synthesized and structurally and magnetically characterized.Compound 1 crystallizes in triclinic system,space group P1 with a = 10.9439(3),b = 11.2823(3),c = 12.2323(4) ?,α = 107.446(3),β = 91.700(3),γ = 91.511(2)°,V = 1439.25(8) ?~3,Z = 1,C_(64)H_(50)N_8O_(14)Dy_2,Mr = 1480.12,Dc = 1.708 g/cm3,μ = 2.653 mm-1 and F(000) = 734.The final R = 0.0366 and w R = 0.0736 for 5816 observed reflections with I 2σ(I).Compound 1 contains the mononuclear [Dy(QLC)_2(1,10-phen)] subunit formed from one 1,10-phen and two QLC-ligands chelating Dy(III) ion.Two mononuclear [Dy(QLC)_2(1,10-phen)] subunits are bridged by a pair of μ_2-OH groups to give a centrosymmetric dinuclear [Dy_2(μ2-OH)_2(QLC)4(1,10-phen)_2] with each Dy(III) ion being eight-coordinated.Detailed susceptibility measurements revealed that compound 1 does not show slow magnetic relaxation under zero direct-current field but exhibits field-induced slow magnetic relaxation under 2 kOe applied field.     

A Co(Ⅱ) Coordination Polymer: Crystal Structure and Treatment Effect on Anxiety and Insomnia by Reducing Sympathetic Excitability

A new coordination polymer, [Co_2(L)_2(H_2O)_2]_n·H_2O(1, H_2L?=?5-(1H-1,2,4-triazol-1-yl)-1,3-benzenedicarboxylic acid), was constructed by hydrothermal condition reaction of Co(NO_3)_2·6H_2O and H_2L at the pH value of 5.6. The as-prepared complex 1 was characterized by elemental analysis, IR and single-crystal X-ray diffraction. Furthermore, a green hand grinding technique has been implemented to reduce the particle size of complex 1 to generate nanoscale 1(denoted as nano 1 hereafter) with spherical morphology. Furthermore, the treatment of the compound on anxiety and insomnia was evaluated. Firstly, the ELISA was used to detect the content of serotonin, gamma-aminobutyric acid in the brain. Besides, the Rat sleep phase detection was determined by pentobarbital synergistic sleep experiment.     

A zinc(Ⅱ) MOF based on secondary building units of infinite wavy-shaped chain exhibiting obvious luminescent sense effects

A new metal-organic framework (MOF),{[Zn_7 (BPS)_4 (OH)_6 (H_2O)_2]·5 H_2O]_n}(1), (H_2 BPS=4,4′-bibenzoic acid-2,2′-sulfone), based on a wavy and infinite chain-shaped secondary building units, has been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction and further confirmed by PXRD, TGA and IR spectrum. The solid-state emission spectra reveal that compound 1 presents strong luminescence emission bands at room temperature. The fluorescent properties of compound 1 in diverse organic solvents indicated that 1 has palpable luminescent sense effects for DMF and DMAC.     

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 [Cu_5(Hpt)_5(H_2O)_2(2,3-PCA)2]n·12 nH_2O(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.