Synthesis,Crystal Structure and Theoretical Calculations of a Cadmium Complex Containing 3-Hydroxybenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane

A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.

Hydrothermal Synthesis, Crystal Structure and Surface Photo-electric Properties of a New Nickel(Ⅱ) 3-D Metalorganic Framework Constructed from the Rigid 1,4-Bis(imidazol-1-yl) benzene Ligand

A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy（SPS）. Complex 1 crystallizes in monoclinic system, space group C2/c with a = 19.5988（6）, b = 9.7531（3）, c = 11.8146（4） ？, β = 96.185（3）°, V = 2245.20（12） ？~3, C_（24）H_（20）N_8NiO_4S, M_r = 575.25, D_c = 1.702 g/cm^3, Z = 4, F（000） = 1184, μ = 1.011 mm-1, the final R = 0.0293 and w R = 0.0702. X-ray diffraction analyses indicated that the center Ni^（2＋） ion is six-coordinated with an O_2N_4 donor set of two μ_2-SO_4^（2–） and four bib ligands, resulting in an ideal octahedral geometry. Topological analysis on complex 1 considers each Ni^（2＋） as a 6-connected node, while bib and sulfate ion as linkers, giving an α-Po topology with short Schl？fli symbol 412·63. In the crystal packing, the components interact with pairs of intermolecular C–H×××O hydrogen bonds. The SPS of 1 indicates that there are positive response bands in the range of 300~600 nm showing photo-electric conversion properties.

Syntheses, Crystal Structures, and Properties of Two Mixed-ligand Coordination Polymers: [Zn(bdc)(1,3-bimb)]_n and {[Mn_2(ox)_2(1,3,5-tib)_(4/3)]·4H_2O}_n

Two new coordination polymers,[Zn（bdc）（1,3-bimb）]n（1） and {[Mn2（ox）2（1,3,5tib）4/3]·4H2O}n（2）（H2ox = oxalic acid,H2bdc = terephthalic acid,1,3-bimb = 1,3-bis（imidazol-1ylmethyl）benzene,1,3,5-tib = 1,3,5-tri（imidazol-1-yl）benzene）,were synthesized and characterized by elemental analysis,IR,powder X-ray diffraction（PXRD）,and thermogravimetric（TG） analyses.X-ray diffracation analysis reveals that two kinds of zigzag chains [Zn（bdc）]n and [Zn（1,3-bimb）]n in compound 1 are interweaved to form a 3D 4-fold interpenetrated 66-dia framework.In compound 2,Mn（1） and Mn（2） are linked via 1,3,5-tib ligands to form two different nets of [Mn6（1,3,5-tib）6 ]n along the ab plane with inner-or outer-shape N–Mn–N angles,which are connected by 1D infinite [Mn2（ox）2 ]n chains via Mn–O bonds to result in a（3,3,3,4,4）-connected（4·8·10）3（4·82）3（4·83·102）6（82·104·3）3（83）4 topology.Moreover,the photoluminescence of 1 has been investigated.The crystal of 1 crystallizes in orthorhombic,space group Pna2 with a = 13.2267（6）,b = 9.1717（4）,c = 17.4492（8）,V = 2116.79（16）3,Z = 4,C22 H18N4O4 Zn,Mr = 467.77,Dc = 1.468 g/cm3,F（000） = 960 and μ（MoKα） = 1.197 mm-1.The final R = 0.0280 and wR = 0.0618 for 3695 observed reflections with I 2（I） and R = 0.0389 and wR = 0.0653 for all data.The crystal of 2 crystallizes in rhombohedral,space group R-3 with a = 22.080（8）,c = 31.19（2）,V = 13167（11） 3,Z = 18,C24 H25 Mn2 N8 O13,Mr = 743.40,Dc = 1.688 g/cm3,F（000） = 6822 and μ（MoKα） = 0.945 mm-1.The final R = 0.0429 and wR = 0.1035 for 5160 observed reflections with I 2（I） and R = 0.0824 and wR = 0.1244 for all data.

Syntheses, Structures and Characteristics of Two New Cu(II) Coordination Polymers Based on 4-tert-butyl-phthalate and Different Bis(1,2,4-triazol-1-yl) Co-Ligands

Two new Cu（Ⅱ） coordination polymers, [Cu2（tbph）2（btb）2]n （1） and {[Cu2（tbph）2- （bth）2]·H2O}n （2）, （H2tbph = 4-tert-butyl-phthalic acid, btb = 1,4-bis（1,2,4-triazol-1- yl）butane, bth = 1,6-bis（1,2,4-triazol-l-yl）hexane）, have been synthesized and characterized by elemental analysis, FT-IR and X-ray single-crystal diffraction. Complex 1 has a 2D sql layer. Complex 2 shows a （3,4）-connected 2D sheet with a （4.6^4.8）（4.8^2） topology. The thermal behavior of the two cor- responding complexes has briefly been investigated.

Syntheses, Structures, and Properties of Three Coordination Polymers: [Cd_2(bpp)_(1.5)(Hbpp)(phen)_2]_n, [Mn_3(Htptc)_2(phen)_2(H_2O)_2]_n, and {[Cu(btc)_(0.5)(1,4-bib)]·2H_2O}_n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n （1）, [Mn3（Htptc）2（phen）2（H2O）2]n （2）, and {[Cu（btc）0.5（1,4- bib）]·2H2O}n（3） （H2bpp = 2,6-bis（4＇-carboxyphenyl）-4-phenylpyridine, H4tptc = terphenyl-2,5,2＇,5＇-tetracar- boxylic acid, H4btc =biphenyl-2,2＇,4,4＇-tetracarboxylic acid, phen =1,10-phenanthroline, and 1,4-bib = 1,4-bis（1H-imidazol-1-yl）benzene）. Their structures have been determined by single- crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D （3,4,5）-connected framework with the Point Schl？fli symbol of （42.6）2（43.62.8）（45.64.8）2. Compound 3 shows an unprecedented 3D （4,4）-connected framework with the Point Schl？fli symbol of （64.82）2（65.8）. Moreover, the luminescent property of 1 has been investigated.

Synthesis,crystal structure,and magnetic properties of a new onedimensional chain antiferromagnet Co(ox)(bib)·H_(2)O(ox=oxalate;bib=1,4-bis(imidazole-1-yl)benzene)

A new one-dimensional(1D)chain antiferromagnet Co(ox)(bib)·H_(2)O 1(ox=oxalate;bib=1,4-bis(imidazole-1-yl)benzene)has been successfully synthesized under hydrothermal condition and characterized by single crystal X-ray crystallography,powder X-ray diffraction,thermogravimetric analysis,Fourier transform infrared(FTIR)spectroscopy,magnetic susceptibility,and heat capacity measurements.The CoII ion is connected by oxalate ions in trans-configuration to form 1D CoII–ox–CoII spin chains,which are further separated by the long organic molecule bib.The magnetic susceptibility curve shows that 1 exhibits a feature of broad maximum around 29 K,indicating strong antiferromagnetic interactions with short spin–spin correlations along the spin chains.However,no long-range order is observed due to the negligible interchain interactions through bib ligand and weak hydrogen bonds,which is further confirmed by the heat capacity data.The intrachain interaction J of−8.4 K is estimated.Both magnetic susceptibility and heat capacity results indicate that 1 exhibits a good 1D magnetism.

Synthesis, Structural Characterization and Fluorescent Properties of a Cadmium Coordination Polymer with 4-Nitrophthalate and 1,4-Bis(imidazol-1-yl)-benzene

A new complex[Cd(nph)(bix)]n(1,H2nph=4-nitrophthalic acid,bix=1,4-bis(imidazol-1-yl)-benzene)has been successfully synthesized under hydrothermal conditions.Its structure has been characterized by elemental analysis,IR spectrum,TG,single-crystal and powder X-ray diffractions.The Cd^2+ion has a distorted octahedral environment with four O atoms from two nph ligands and two N atoms from two bix ligands.Each bix acts as a cis-conformation bridging ligand to link the neighboring[Cd2(nph)]subunit to form tetranuclear subunits with 42-ring,which are bridged again by bix ligands to yield a two-dimensional network structure.It was stabilized by C–H···O hydrogen bonding andπ-πinteractions,and extended into a 3D supramolecular architecture.Moreover,the luminescent properties of complex 1 have been investigated in the solid state.

Two Three-dimensional Supramolecular Complexes Assembled by 2-Chlorinebenzoic Acid and Bis(imidazol)Ligands:Syntheses,Structures and Fluorescent Properties

Two new three-dimensional supramolecular complexes, namely, [Cd(cba)2(bib)]n(1) and [Zn(cba)2(bib)]2 n(2)(Hcba = 2-chlorinebenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane)were hydrothermally designed and synthesized. Their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, single-crystal and powder X-ray diffraction. Complex 1 exhibits a one-dimensional zigzag chain and complex 2 shows a zero-dimensional structure, which were further extended into three-dimensional supramolecular structures through hydrogen bonds and π-π stacking interactions.

A Cu(Ⅱ) Coordination Polymer with 5-Tert-butyl Isophthalate Linker:Synthesis,Crystal Structure,and Magnetic Properties

A new Cu（Ⅱ） metal-organic coordination polymer, {[Cu2（tbip）2（bie）2]·H2O}n （1, H2tbip = 5-tert-butyl isophthalic acid, bie = 1,2-bis（imidazol-1 ＇-yl）ethane）, was assembled under hydrothermal conditions by the reactions of Cu（Ⅱ） acetate with H2tbip and bie. Complex 1 was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in triclinic, space group P1, with a = 9.9145（10）, b = 13.2211（13）, c = 15.4363（15） nm, a = 87.0250（10）, β = 88.3220（10）, γ = 83.8240（10）°, V= 2008.4（3） nm3, Z = 2, Dc = 1.505 Mg/m3, F（000） = 944, g = 1.125 mm^-1, S = 1.030, the final R = 0.0336 and wR = 0.0790. The results reveal that complex 1 is a two-dimensional layered structure. In addition, magnetic properties of I were also investigated.

Syntheses,Crystal Structures and Fluorescent Properties of Two Zinc Complexes Assembled by Bis(imidazol)Ligands

Two new complexes[Zn(nph)(bix)]n·nH2O(1)and[Zn(nba)2(bix)]n(2)(H2nph=4-nitrophthalic acid,Hnba=4-nitrobenzoic acid,bix=1,4-bis(imidazol-1-yl)-benzene)have been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,fluorescence spectrum,single-crystal and power X-ray diffraction.Complex 1 exhibits a three-dimensional(3D)framework,which is stabilized through C–H…O hydrogen bonds andπ-πstacking interactions.Complex 2 shows a zero-dimensional structure,which is further extended into a three-dimensional supramolecular structure through C–H…O and C–H…N hydrogen bonding interactions.