Synthesis and Crystal Structure of a New Zn(Ⅱ) Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylate

A new Zn(Ⅱ) coordination polymer [Zn3(btec)(OH)2(H2O)2]n (1, btec = 1,2,4,5- benzenetetracarboxylate) has been synthesized by hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in mono- clinic, space group C2/c, with a = 19.580(3), b = 5.0137(8), c = 15.975(3), β = 121.629(2)°, V = 1335.3(4)3, C10H8O12Zn3, Mr = 516.27, Z = 4, Dc = 2.568g/cm3, μ = 5.419 mm-1, F(000) = 1016, R = 0.0590 and Rw = 0.1279 for 1110 observed reflections (I > 2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(Ⅱ) atoms which are connected through the bridging carboxylate oxygen atoms of the btec ligands and μ2-bridging oxygen atoms of water molecules to generate an infinite one-dimensional chain. The adjacent chains are linked together through the benzene rings of the btec ligands to form a two-dimensional polymeric network. The adjacent two-dimensional layers are further connected together by the benzene rings of btec ligands to give the final three-dimensional structure. The benzene rings act as pillars between two layers.     

Synthesis,Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn(II) coordination polymer [Zn3(BTC)2(4,4'-bpy)(CO)2]n(1, H3 BTC =1,3,5-benzenetricarboxylic acid, 4,4'-bpy = 4,4'-bipyridine) has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262(3), b = 18.838(5), c =15.083(4) A, β = 99.203(4)o, V = 2878.3(14) A3, C30H14Zn3N2O14, Mr = 822.54, Z = 4, Dc = 1.898g/cm3, μ = 2.561 mm-1, F(000) = 1640, R = 0.0363 and w R = 0.0932 for 2828 observed reflections(I 2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(II) atoms which are connected by BTC3- ligands and 4,4'-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.     

Synthesis and Crystal Structure of Salicylyl-4-phenyl Thiosemicarbazide Lead with a Two-dimensional Network

A two-dimensional lead complex, [Pb(C14N3O2H12S)(NO3)]n·nH2O, was prepared by the reaction of salicylyl-4-phenyl thiosemicarbazide and lead nitrate. The compound (C14H13N4O6PbS, Mr=572.53) crystallizes in the monoclinic space group P21/c with a=11.2984(2), b=15.6628(7), c=11.1118(2), β= 113.564(2)n, V=1802.43(10)3, Dc=2.110 g/cm3, Z=4, μ(MoKα)= 9.515 mm·1, F(000)=1084, the final R=0.0394 and wR=0.0701 for 2552 observed reflections with I > 2σ(I). The Pb(II) ion displays a distorted octahedron in which the hypothesized stereochemically active lone pair occupies the apex. The compound exhibits a two-dimensional network structure formed by the zigzag one-dimensional chains joined by two μ-O of two nitrate groups in overlapping. A large ring exists in the two-dimensional layers. The TGA of the title compound has been studied.     

One Pillared Layered Zn(Ⅱ) Coordination Compound Based on 2,6-Naphthalenedicarboxylic Acid: Synthesis,Structure and Luminescent Property

One new pillared layered zinc hydroxide {Zn_4(OH)_6(ndc)·2(H_2 O)}_n,(H_2 ndc =2,6-na-phthalenedicarboxylic acid) has been achieved under hydrothermal conditions by using2,6-na-phthalenedicarboxylic acid, 2,4-diami-6-phenyl-1,3,5-triazine as well as Zn(OAc)_2·2 H_2 O,and structurally characterized by X-ray single-crystal diffraction, IR spectra, elemental analysis,powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The X-ray single-crystal diffraction proves that the title compound is in monoclinic system, space group P2_1/c with a =16.362(8), b = 9.324(5), c = 5.364(3) ?, β = 99.081(9)°, V = 808.1(7) ?~3, D_c = 2.522 g/cm~3, M_r =613.73, Z = 2, F(000) = 608, μ = 5.935 mm~(-1), GOOF = 1.050, R = 0.0469 and wR(Ⅰ 2σ(Ⅰ)) =0.1291. In the title compound, the tetrahedral and octahedral zinc atoms are connected by μ_3-OH groups to form zinc hydroxide inorganic layers extending parallel to the bc-plane. The adjacent layers are pillared by the connection of Zn2 atoms with ndc~(2-)ligands to construct a three-dimensional(3D) structure; meanwhile, the interactions of five hydrogen bonds make the 3D network structure more stable. Furthermore, the title compound exhibits luminescent property at solid state.     

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).     

Synthesis and Crystal Structure of a Luminescent Compound 5-（1H-benzoimidazol-2-yl）- 3H-[ 1,2,3 ] triazole-4-carboxylic Acid

The title compound, 5-(1H-benzoimidazol-2-yl)-3H-[1,2,3]triazole-4-carboxylic acid (C10H7N5O2·C3H7NO, Mr=302.30), has been synthesized and characterized by FT-IR and ESI-MS, 1 H-NMR spectroscopy and X-ray single-crystal diffraction. Crystal structure of the title compound was grown from DMF by slow diffusion at room temperature. Crystal data: orthorhombic structure, space group Pna21 with a=6.9635(3), b=19.4398(7), c=30.6165(12), V=4144.5(3)3, Z=12, Dc=1.454 g/cm 3, μ(MoKα)=0.108 mm-1, and F(000)=1896. The structure was refined to R=0.0450 and wR=0.0975 for 3578 observed reflections with I>2σ(I). The intermolecular hydrogen bonds and π-π stacking further stabilize the structure.     

Synthesis and Crystal Structure of 4-Arylamino-6-chloropyrido[3,2-d]pyrimidine

The title compounds 4a～c were synthesized and characterized by IR,NMR and MS.The crystal structure of C16H13ClN4O2·HBr·H2O(I),the quaternary ammonium salt of 4c,was determined by X-ray diffraction analysis.I crystallizes in triclinic,space group P1 with a = 8.3121(8),b = 9.3885(8),c = 13.2903(12),α = 106.788(2),β = 95.204(3),γ = 110.871(2)o,V = 905.81(14)3,Z = 2,C16H16BrClN4O3,Mr = 427.68,Dc = 1.568 g/cm3,F(000) = 432.00,μ = 2.446 mm-1,R = 0.0496 and wR = 0.127.X-ray analysis reveals that C(15) in the BrCH2COOH molecule binds to the N(1) of pyrimidine ring to form the quaternary ammonium salt.Two adjacent I molecules are connected by hydrogen bonds through carboxylate oxygen,water molecule and hydrobromic acid.     

Synthesis and Crystal Structure of a Two-dimensional Cadmium(Ⅱ) Coordination Polymer:[Cd(AIP)(Bpy)]_n·nBpy(H_2AIP=5-Aminoisophthalic Acid,Bpy=2,2′-Bipyridyl)

A two-dimensional coordination polymer, [Cd(AIP)(Bpy)]n·nBpy, was hydrother- mally synthesized by the reaction of hydrate cadmium acetate with 5-aminoisophthalic acid, lithium hydroxide, vanadiumpentoxide, sodium chloride and 2,2′-bipyridyl in water solution. It crystallizes in orthorhombic, space group C2221, absolute structure parameter 0.00(7), with a = 15.336(4), b = 22.390(6), c = 14.257(3) , V = 4896(2)3, C28H21CdN5O4, Mr = 603.90, Z = 8, F(000) = 2432, Dc = 1.639 g/cm3, μ = 0.939 mm–1, T = 298(2) K, S = 1.001, R = 0.0296 and wR = 0.0813 for 5522 observed reflections (I > 2σ(I)). In the title complex, each 5-aminoisophthalate ligand bridges three cadmium(II) ions to form a two-dimensional layer structure.     

Solvothermal Synthesis and Crystal structure of a Two-dimensional Cd（Ⅱ） Complex Based on a Flexible Carboxylate Ligand

A two-dimensional Cd(II) coordination polymer, [Cd(dtb)]n (dtb=5,5-dithiobis(2- nitrobenzoic acid), has been solvothermally synthesized and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/c space group, with a=10.7147(10), b=7.4518(7), c=22.053(2), β=95.477(2)o, V=1752.7(3)3, Z=4, Mr=524.74, Dc=1.989 g/cm3 and F(000)=1032. The final R=0.0453 and wR=0.1201 for 2950 observed reflections with I>2σ(I). In the complex, the Cd(II) ion is coordinated with six oxygen atoms from four different carboxylate groups of dtb ligands and one lattice water molecule. The adjacent Cd centers are interconnected by the flexible carboxylate ligand to form a two-dimensional (2D) structure.     

Studies on the Synthesis,Crystal Structure and Quantum Chemistry of Di(o-cyanobenzyl)tin Bis(quinoline-2-carboxylate)

Di(o-cyanobenzyl)tin bis(quinoline-2-carboxylate)was synthesized by the reaction of tri(o-cyanobenzyl)tin chloride with quinoline-2-carboxylic acid.The molecular structure of the compound Was characterized by elemental analysis,IR,1H NMR and X-ray diffraction.Crystal data for the compound:triclinic,space group P1,a=0.80734(7),b=1.00681(9),c=1.04811(9)nm,α=81.7570(10),β=7.7240(10),γ=81.2850(10)°,V=0.77581(12)nm3,Z=1,Dc=1.488 g/cm3,μ(MoKa)=0.870 mm-1 and F(000)=350.1 The final R=0.0204 and wR=0.0530 for 2677 observed reflections with I＞2σ(I),and R=0.0208 and wR=0.0532 for all reflections.The molecular structure adopts a distorted octahedral geometry around the Sn atom.The title compound molecules are connected via hydrogen bonding interactions to form a 3D network structure.Quantum chemistry calculation study on the title compound has been performed by means of G98W package at the Lanl2dz basis set.The stability of the compound,orbital energies and some frontier molecular orbital composition characteristics have also been investigated.     

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver（I） Cluster

A new hexanuclear silver(I) compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound crystallizes in monoclinic,space group P2 1 /c with a=16.101(4),b=24.855(7),c=14.492(4),β=109.730(5)°,V=5459(3)3,C 90 H 102 Ag 6 N 24 O 6 S 6,M r=2455.54,D c=1.494 g/cm 3,μ(MoKα)=1.228 mm-1,F(000)=2472,Z=2,the final R=0.0761 and wR=0.1507 for 5258 observed reflections (I > 2σ(I)).In the structure,the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag 6 L 6 cluster.Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.     

A New One-dimensional Chain-like Ag（I） Complex with Schiff Base Ligand Containing 4-Amino-1,2,4-triazole

The title compound,poly[N-[1-(3-pydidyl)ethylidene]-4H-1,2,4-triazol-4-amine sil-ver(I) tetrafluoroborate],[Ag(C9H9N5)(BF4)]n,is the result of complexing Ag cation with N-[1-(3-pydidyl)ethylidene]-4H-1,2,4-triazol-4-amine (L),and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group C2/c with a= 18.899(6),b=9.882(2),c=15.472(4),β=120.158(3)°,V=2498.5(11)3,C9H9AgBF4N5,Mr= 381.89,Dc=2.031 g/cm3,μ(MoKα)=1.659 mm-1,F(000)=1488,Z=8,the final R=0.0441 and wR=0.0619 for 1094 observed reflections (I 2σ(I)).In the structure,ligand L bridges the two metal Ag(I) centers in a bidentate fashion and each metal ion coordinates with two nitrogen atoms,forming a one-dimensional rectangular chain.The neighboring chains are connected by two additional Ag-N weak interactions into a 3D framework structure.The title compound shows blue fluorescence property at room temperature.     

Synthesis,Crystal Structure and Photoluminescent Property of a New Zn(Ⅱ) Complex Based on 3,4-Bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

The coordination polymer[Zn_(1.5)(2,2?,4??-tpt)(tpa)_2]_n(2,2?,4??-tpt=3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole,H_2tpa=terephthalic acid)has been obtained by solution evaporation method 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=10.331(3),b=10.596(1),c=14.966(3)?,β=99.029(0)o,V=1448.86(6)?~3,Z=2,D_c=1.668g/cm~3,μ=1.320 mm~(-1),F(000)=740,R=0.0359 and w R=0.0841 with I2σ(I)).In this polymer,the asymmetric unit contains two crystallographically independent Zn(II)ions in different coordination environments.Zn(1)ion is five-coordinated,forming a distorted tetragonal pyramidal geometry,while the Zn(2)ion is six-coordinated to get a distorted octahedral geometry.Each Zn(II)ion is linked by 2,2?,4??-tpt and H_2tpa ligands,forming an infinite 2D structure.The existence of O(8)–H(8)···O(2)hydrogen bonding interactions leads the 2D chains to generate a 3D structure.In addition,1 shows strong photoluminescent emissions in the solid state at room temperature,so it can be used as potential optical materials.     

Synthesis and Crystal Structure of 1,4-Dimethyl-2,5-di{[2’-(3-pyridylmethylamino-formyl)phenoxyl]methyl}benzene Perchlorate

The title compound, 1,4-dimethyl-2,5-di{[2’-(3-pyridylmethylaminoformyl)phenoxyl]- methyl}benzene perchlorate (C36H36Cl2N4O12, Mr = 787.59), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366(4), b = 15.159(4), c = 16.443(5), V = 3580.9(17)3, Z = 4, Dc = 1.461 g/cm3, μ = 0.253 mm-1, F(000) = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections (I > 2σ(I)). In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.     

Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb(SIP)(H2O)5]2(bpy)3(H2O)}n (NaH2SIP= 5-sulfoisophthalic acid monosodium salt and bpy=4,4'-bipyridyl), has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a= 30.6840(1), b=10.9206(2), c=17.4967(3), β=111.931(1)o, V=5438.65(14)3, Z=4, C46H52N6O25S2Tb2, Mr=1470.90, Dc=1.796 g/cm3, μ=2.747 mm-1, F(000)=2928, the final R= 0.0654 and wR=0.1322 for 3806 observed reflections with I > 2σ(I). In the neutral [Tb(SIP)(H2O)5]2 motif, the Tb(III) ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H···N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.     

Synthesis and Crystal Structure of a One-dimensional Silver(I) Coordination Polymer with 4,4'-Bipyridine

The title compound, {[Ag2(bipy)2(H2O)2]·pydc·2H2O}n (bipy=4,4'-bipyridine, pydc= pyridine-3,5-dicarboxylate), has been synthesized by the reaction of Ag2O with pydc and bipy in CH3OH solution. It crystallizes in the monoclinic system, space group C2/c with a=21.419(8), b=7.515(3), c=18.070(7), β=108.273(6)°, Mr=765.27, V=2761.9(17)3, Z=4, Dc=1.840 g/cm3, F(000)= 1528, μ=1.478 mm-1, the final R=0.0307 and wR=0.0681. The structure determined demonstrated that the Ag(I) is three-coordinated by two nitrogen atoms from bipy and one water molecule, forming a one-dimensional coordination polymer [Ag2(bipy)2(H2O)2]n2n+, which is further linked to generate a two-dimensional layer structure via Ag…Ag attractions.     

A New Two-dimensional Zinc Coordination Polymer Constructed by 1,3-Bis(4-pyridyl)-propane and Terephthalate: Synthesis and Crystal Structure

A new zinc coordination polymer, [Zn2(bpp)(tpa)2H2O] 1 (bpp=1,3-bis(4-pyridyl)-propane and tpa=terephthalate) has been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group P2/c with a=18.348(2), b=10.9080(14), c=13.7924(18), β=98.156(2)°, V=2732.5(6)3 , Z=4, C29H24N2O9Zn2 , Mr=675.24, Z=4, F(000)=1376, Dc=1.641 mg/m3 , μ=1.815 mm-1 , the final R=0.0443 and wR=0.0769 for 2715 observed reflections (I>2σ(I)). The title complex exhibits a two-dimensional (4, 4) sheet structure which is further stacked through face-to-face π-π interactions between the monodentately coordinated pyridine ring of bpp ligand and the phenyl ring of terephthalate ligand to form a 3-dimensional supramolecular structure. Thermogravimetric analyses show that the host framework of the complex is thermally stable up to ca. 400 ℃.     

The First Two-dimensional Supramolecular Network Constructed by Na（Ⅰ） with 2-Methylimidazole-4,5-dicarboxylate Building Blocks

The title complex [Na(H2MIA-)(H2O)](1,H3MIA = 2-methyl-1H-imidazole-4,5-dicarboxylic acid) has been synthesized by hydrothermal synthesis and structurally characterized by X-ray crystallography.Compound 1 crystallizes in orthorhombic,space group ibam with a = 14.4737(19),b = 17.553(2),c = 6.5285(9),V = 1658.6(4) 3,C6H7N2NaO5,Mr = 210.12,Z = 8,Dc = 1.675 g/cm3,F(000) = 864,μ = 0.188 mm-1,λ(MoKα) = 0.071073 ,R = 0.0383 and wR = 0.0987 for 1046 observed reflections(I > 2σ(I)).In the structure of 1,each coordination water coordinates with two Na(I) ions at the same time and links the neighboring Na(I) ions to form a one-dimensional Na(I)-water chain.Each H2MIA-ligand links the neighboring Na(I) of Na(I)-water chain to form a novel two-dimensional supramolecular network.The 2-D network is stabilized by O-H…N hydrogen bonds and π-π interaction.The 2D network is further linked via O-H…O hydrogen bonds to yield a three-dimensional framework.     

A Novel 3D Supramolecular Framework of Poly[(5-(oxidediphenylphosphino)isophthalate)zinc(Ⅱ)]: Syntheses and Structure

A novel metal-organic framework, namely [Zn(C20H13O5P)]n(1), has been hydrothermally synthesized through the reaction of 5-(oxidediphenylphosphino)isophthalic acid(H2L) with Zn(Ⅱ) salt. The title compound crystallizes in monoclinic, space group P21/c with a = 11.0966(10), b = 14.5651(14), c = 14.7311(15), β = 130.022(6)o, C20H13O5 PZn, Mr = 429.64, V = 1823.3(3) 3, Dc = 1.565 g/cm3, F(000) = 872, μ = 1.463 mm-1, S = 1.054 and Z = 4. The final R = 0.0270 and wR = 0.0739 for 2769 observed reflections with I 2σ(I). In the title complex, the Zn2(CO2)2 binuclear clusters are linked by L2- ligands to result in a pillared layer structure in the bc plane, which is a(4,4)-net composed of helical chains with opposite chirality by sharing Zn2(CO2)2 units. Adjacent layers are further associated together through Zn–O bonds involving the metal center and the oxygen atom of P=O group to achieve a 3D architecture, in which one-dimensional quadrangled channel displays the interweaving of two pairs of coaxial double-helical chains with opposite chirality. The luminescence property and thermogravimetric analysis of the title complex were investigated.     

Synthesis and Structure Analysis of N-（Dehydroabietyl）maleamic Acid

N-(Dehydroabietyl)maleamic acid was synthesized from dehydroabietylamine and maleic anhydride.Its structure was characterized by IR,1 H-and 13 C-NMR spectra.The stereo structure of the title compound was also unambiguously confirmed by X-ray crystal structure analysis.The white crystal crystallizes in the monoclinic system,space group P2 1 with a=12.075(2),b=10.377(2),c=17.840(4),β=100.31(3) °,V=2199.3(8) 3,R=0.0618 and wR=0.1437.Two crystallographically independent molecules with different conformations co-exist in the unit.In each molecule,the two cyclohexane rings form a trans ring junction with chair and half-chair conformations,respectively.The C=C double bond between two carbonyl groups is in a Z configuration.Intermolecular and intramolecular hydrogen bonds coexist to stabilize the structure.