Syntheses,Crystal Structures,and Magnetic Properties of the Cobalt(Ⅱ) and Nickel(Ⅱ) Coordination Polymers Constructed from 5-Halonicotinate and 2,2ˊ-Biimidazole

Two coordination polymers, namely [Co(5-Clnic)2(H2biim)]n 1 and {[Ni(5-Clnic)(Hbiim)]·H2O}n 2(5-Clnic H = 5-halonicotinic acid, H2 biim = 2,2ˊ-biimidazole), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N–H···O and O–H···O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.     

Synthesis,Crystal Structures and Magnetic Properties of Cobalt（II） and Manganese（II） Coordination Polymers Constructed from 5-（Pyridin-4-yl）isophthalate Ligands

Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group Pī with α = 7.2188（7）, b = 10.0835（8）, c = 10.2069（7） ？, α = 113.713（7）, β = 99.490（7）, γ = 104.516（8）o, V = 628.24（9） ？3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ（MoKα） = 1.395 mm–1, F（000） = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections （I 〉 2σ（I）） and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with α = 12.9185（3）, b = 10.4343（2）, c = 31.7650（6） ？, β = 101.282（2）o, V = 4199.08（13） ？3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ（MoKα） = 5.447 mm–1, F（000） = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections （I 〉 2σ（I）） and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt（II） subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H… hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H… hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Hydrothermal Syntheses and Crystal Structures of Zn(Ⅱ) and Co(Ⅱ) Complexes Constructed from 5-Methoxyisophthalic Acid and 1,10-Phenanthroline Ligands

Two new one-dimensional coordination polymers,[Zn(L)(phen)]n 1 and {[Co2(L)2(phen)2]·2H2O}n 2(H2L=5-methoxyisophthalic acid,phen=1,10-phenanthroline),have been obtained by hydrothermal conditions.According to their single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P2/c with a=8.9195(11),b=12.3620(15),c=17.0211(18),β=106.690(5)o,V=1797.7(4)3,the final R=0.0298 and wR=0.0715 for 3351 independent reflections with Rint=0.0353.Complex 2 crystallizes in the monoclinic system,space group C2/c with a=24.981(4),b=11.1204(19),c=18.125(3),β=132.5620(10)o,V=3708.5(11)3,the final R=0.0349 and wR=0.0914 for 3424 independent reflections with Rint=0.0214.Both 1 and 2 show L-bridged one-dimensional chain.1 and 2 are further assembled by π-π and hydrogen bonding interactions into 2-D layer structures,and they also display 3-D supramolecular frameworks through their other hydrogen bonds.Zn(Ⅱ) ion is five-coordinated with a distorted trigonal bipyramidal coordination geometry,while Co(Ⅱ) ion is six-coordinated and resides in a distorted octahedral coordination geometry.Additionally,complex 1 shows fluorescence in the solid state at room temperature.     

Syntheses and Crystal Structures of Three Novel Zn~Ⅱ-sulfonyldibenzoilate Coordination Polymers

Three coordination polymers based on the V-shaped 4,4＇-dicarboxybiphenyl sulfone （H2sdba） ligands, [Zn3（μ-OH）2（sdba）2]n·2nH2O 1, [Zn2（sdba）2（4,4＇-bipy）]n·2nH2O 2 and [Zn3（sdba）3（py）2]n·n（py）·nH2O 3 （4,4＇-bipy = 4,4＇-bipydine）, were hydrothermally synthesized and structurally characterized. Complex 1 features the 2D planes constructed by the sdba ligands linking infinite Zn-O-C SBUs. The 4,4＇-bipy ligands in 2 bridge the Zn^II-sdba chains into interpenetrated 2D planes. The 3D network of α-Po topology in 3 is built from tri-nuclear Zn3 units with a [Zn3（OOC）6] structure. The intense blue and yellow luminescence was observed in complexes 1～3 which may result from ligand-to-metal charge transfer （LMCT）.     

Two Novel Zn（ll）-biphenyl-3,4,5-tricarboxylate Coordination Polymers： Syntheses,Crystal Structures and Luminescence Properties

Two novel Zn（II）-organic frameworks [（CH3）2NH2][Zn（BPT）]＇0.5DMF （1） and [Zn2（HBPT）2（1,4-bis）] （2） （H3BPT = biphenyl-3,4,5-tricarboxylic acid, 1,4-his = 1,4-bis（1H- imidazol-1-yl）butane） have been synthesized under solvothermal conditions, and characterized by IR spectroscopy, powder X-ray diffractions （PXRD） and single-crystal X-ray diffractions. Complex l displays a rtl rutile 3,6-connected network with {4.62}2{42.610.83} topology, while with the 1,4-his secondary ligand being introduced into the assembly, a different structure 2 has been obtained. Compound 2 forms a 2D layered framework through linking by both BPT and 1,4-bis ligands, which is further stacked via hydrogen-bonding interactions to a three-dimensional supramolecular architecture. Furthermore, thermal analyses （TGA） and photoluminescent properties of I and 2 are also investigated in detail.     

Syntheses,Crystal Structures,and Magnetic Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed from Pyridine-tricarboxylate Ligand

Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3~(10).5.6~4)4(3~(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.     

Synthesis, Crystal Structure and Magnetic Properties of a Novel Azide-bridged Copper（Ⅱ） Coordination Polymers Containing Nitroxy Nitroxide

A novel azide-bridged copper(Ⅱ) coordination polymer, [Cu3(NITpPy)4(N3)6]n (NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl), was structurally and magnetically characterized. It crystallizes in the triclinic space group P with a = 7.6932(10), b = 14.5556(19), c = 16.122(2) , α = 108.443(2), β = 95.251(2), γ = 104.236(2)°, V = 1631.7(4) 3, C48H64Cu3N30O8, Mr = 1379.87, Z = 1, Dc = 1.404 g/cm3, μ(MoKα) = 1.041 mm-1, F(000) = 713, the R = 0.0510 and wR = 0.1185 for 4285 observed reflections with I > 2σ(I). X-ray analysis reveals that the Cu(Ⅱ) ions are linked by nitrogen atom of μ1,1 azido ligands to form a Cu-Cu-Cu unit. The units are linked by μ1,3 azido ligands through a bridging style to form a one-dimensional coordination polymer. The variable-temperature magnetic susceptibility data of the complex show ferromagnetic interactions in the complex.     

Synthesis,Crystal Structure and Luminescent Properties of a Mn（Ⅱ） Complex Constructed from 2,2＇-Bibenzimidazole

A new complex associated with Mn ion,[Mn(Hbibm)(SO4)]·0.5H2O(1,Hbibm= 2,2'-bibenzimidazole),was prepared under solvothermal conditions,and characterized by single-crystal X-ray diffraction,elemental analysis and IR spectra.The complex belongs to the triclinic system,space group P1 with a=8.9250(5),b=12.8022(8),c=13.3505(8),α=66.614(2),β= 72.567(2),γ=80.627(2)°,V=1334.1(1)3,Z=1,Dc=1.565 g/cm3,S=0.996,μ=0.628 mm-1,F(000)=644,R=0.0447 and wR=0.0586 for 5155 observed reflections(Ⅰ > 2σ(Ⅰ)).Complex 1 is a mononuclear Mn(II) complex.The π-π interactions and interchain hydrogen-bonding interactions further extend the mononuclear for 1,generating a 3D supramolecular architecture.Complex 1 shows strong blue fluorescent emissions in the solid state upon 395 nm photo-excitation at room temperature.     

Syntheses and Crystal Structures of Co(Ⅱ)Complexes with 5-Tert-butyl Isophthalic Acid

<正>Two new Co(Ⅱ)coordination polymers {[Co(Htbip)_2(H_2O)_4]·(H_2O)}_n 1 and {[Co_2(tbip)_2(bpa)_(1.5)](H_2tbip)}_n 2(H_2tbip=5-tert-butyl isophthalic acid,bpa=1,2-dis(4-pyridyl) ethane)have been synthesized under hydrothermal conditions and characterized by elemental analysis,IR spectroscopy and X-ray diffraction.Compound 1 exhibits a water-bridged 1-D linear chain which is extended by hydrogen bonds into a 3D supramolecular network,while compound 2 has a dinuclear unit extended by bpa ligand to form a 2-D layer.     

以1-（3-羧苯基）-5-甲基-1氢-1，2，3-三唑-4-羧酸为配体构筑的两个配合物的合成、晶体结构及性质

1-（3-羧苯基）-5-甲基-1氢-1,2,3-三唑-4-羧酸为配体与锰金属盐、锌金属盐在水热合成法得到2个配位聚合物：{Mn（cpmtc）₂（H₂O）₂}_n（1）,{Zn（cpmtc）₃（H₂O）}_n（2）。通过单晶衍射仪测得这2个晶体结构,配位聚合物1为单斜晶系,P2₁/c空间群;a=1.18352（19）nm,b=1.19801（19）nm,c=0.99876（16）nm,β=113.201°。配位聚合物2属于单斜晶系,P2₁/c空间群;a=1.0233（3）nm,b=1.1720（4）nm,c=1.0233（3）nm,β=92.8700°。除此之外,这2个配位聚合物通过红外和荧光进行表征。     

Two New Cu(Ⅱ) Coordination Polymers Based on 2,5-Furandicarboxylic Acid and 2,2'-bipyridine:Synthesis and Crystal Structure

Two new Cu(Ⅱ) coordination polymers,[Cu(FDA)(BPY)(H2O)]n(1) and {[Cu(FDA)(BPY)(H2O)]·2H2O}n(2)(H2FDA = 2,5-furandicarboxylic acid,BPY = 2,2-bipyridine),have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR.Compound 1 crystallizes in monoclinic,space group P21/c,with a = 7.5915(15),b = 8.4050(17),c = 24.204(6) ,β = 99.05(3)°,V = 1525.1(6) 3,Dc = 1.706 g/cm3,C16H12CuN2O6,Mr = 391.82,F(000) = 796,μ(MoKα) = 1.470 mm–1,Z = 4,R = 0.0633 and wR = 0.1059 for 2389 observed reflections(I 2σ(I)),R = 0.0738,and wR = 0.1098 for all data.Complex 2 belongs to triclinic space group P1 with a = 8.8660(18),b = 8.9112(18),c = 12.525(3) ,α = 88.41(3),β = 69.38(3),γ = 66.95(3)°,V = 845.2(3) 3,Dc = 1.681 g/cm3,C16H16CuN2O8,Mr = 427.85,F(000) = 438,μ(MoKα) = 1.342 mm–1,Z = 2,R = 0.0290 and wR = 0.0690 for 2767 observed reflections(I 2σ(I)),R = 0.0329 and wR = 0.0706 for all data.Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands,which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.     

Syntheses and Crystal Structures of Two Coordination Polymers of Cobalt and Cadmium Assembled by 4,4ˊ-(Ethane-1,2-diyldioxy)dibenzoic Acid

Two new metal-organic coordination polymers [Co0.5（Heoba）（bib）0.5]2n（1） and [Cd（eoba）（phen）]n（2）（H2eoba = 4,4-（ethane-1,2-diyldioxy）dibenzoic acid, bib = 1,4-bis（imidazol-1-yl）-butane, phen = 1,10-phenanthroline） have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. Complex 1 is a 2D network structure, and complex 2 exhibits a 3D network structure. Moreover, the luminescent property of complex 2 has been investigated in the solid state.     

Synthesis,Crystal Structure and Magnetic Properties of a Coordination Polymer Based on Iron(Ⅱ) Carboxylate Helical Chains [Fe(bpdc)(H_2O)_2]n

A coordination polymer based on iron(II) carboxylate helical chains [Fe(bpdc)(H2O)2]n 1 has been constructed hydrothermally using H2bpdc (H2bpdc = 2,2'-bipyridine-4,4'-dicarboxylic acid), pyridine and FeSO4·7H2O. Its crystal structure reveals that the Fe(Ⅱ) ion adopts a slightly distorted octahedron. The carboxylates of bpdc ligands alternately bridge the Fe(Ⅱ) cations to form 1D infinite helical chains. The Fe···Fe intrachain distance is 4.8246(6) . The adjacent chains are further interlinked by the coordination of bpdc ligands and hydrogen bonding to form a 3D framework. Magnetic studies for complex 1 show weak antiferromagnetic coupling between the Fe(Ⅱ) ions. The best-fit for χM T vs. T with a Hamiltonian∑∑==iBiiHJSi SigHS11 leadsto g = 2.314(4) and J = -0.68(1) cm-1.     

Two New Coordination Polymers Assembled with a Functionalized Ligand：Syntheses and Crystal Structures

Two new transition-metal organic coordination polymers [M(mna)2](M = Cd(1),Zn(2);mna = 2-mercaptonicotinic anion) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction along with IR and elemental analyses.Compound 1 is generally a one-dimensional linear structure bridged through the sulfur donor of mna ligand,while 2 is a one-dimensional zigzag chain ligated via the oxygen donor of mna ligand.These compounds further result in three-dimensional structures via intermolecular π...π stacking interactions and/or hydrogen bonding interactions.The two compounds were structurally determined by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic space group P21/c with a = 3.730(3),b = 13.973(12),c = 12.380(11) ,β = 97.953(18)°,V = 639.0(10) 3,Z = 2,CdC12H8O4N2S2,Mr = 420.72,Dc = 2.187 g/cm3,F(000) = 412,Rint = 0.0252,T = 293(2) K,μ = 2.052 mm?1,the final R = 0.0269 and wR = 0.0586 for 1377 observed reflections with I > 2σ(I).Complex 2 belongs to monoclinic space group P21/c with a = 13.376(2),b = 12.8429(14),c = 7.4856(10) ,β = 96.190(10)°,V = 1278.5(3) 3,Z = 4,ZnC12H8O4N2S2,Mr = 373.69,Dc = 1.941 g/cm3,F(000) = 752,Rint = 0.0414,T = 293(2) K,μ = 2.264 mm?1,the final R = 0.0418 and wR = 0.0966 for 2396 observed reflections with I > 2σ(I).     

Three 3D M~Ⅱ (M = Co,Ni, Zn) Supramolecular Polymers Constructed from O-vanillic Acid: Synthesis,Crystal Structure and TGA

The title compounds, [Co(H2O)6](OVA)2·2H2O 1, [Ni(H2O)6](OVA)2·2H2O 2 and [Zn(OVA)2·2H2O] 3 (HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate), were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc(Ⅱ) atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc(Ⅱ) atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) atoms.     

Synthesis and Crystal Structure of a New(6,3)-Connected Ni(Ⅱ) Coordination Polymer

The coordination polymer [Ni(dpa)(bpp)]n(H2dpa = 2,4'-biphenyl-dicarboxylic acid,bpp = 1,3-di(4-pyridyl)propane) was hydrothermally prepared and characterized by single-crystal X-ray diffraction,FTIR spectra,elemental analysis and thermal analysis.The crystal is of triclinic system,space group P1 with a = 12.516(5),b = 12.943(5),c = 15.130(5) ,α = 94.331(5),β = 91.827(5),γ = 108.382(5)°,C54H44N4Ni2O8,Mr = 497.18,V = 2315.3(15) 3,Dc = 1.426 g/cm3,F(000) = 1032,μ = 0.875 cm-1,Z = 2,the final R = 0.0496 and wR = 0.1100 for 5365 reflections with Ⅰ 2σ(Ⅰ).X-ray diffraction analysis reveals that the carboxylate group of 2,4'-diphenic acids acting as bridging ligands adopts two coordination modes:bis-mondentate and bidentate chelating.The compound exhibits a two-dimensional(6,3)-connected architecture.