Catena-dichloro(4,4?-dimethyl-2,2?-bipyridine) Cadmium(II), a New One-dimensional Chain with Blue Fluorescent Emission

A new μ-chloro-bridged one-dimensional coordination polymer [Cd(dmbpy)Cl2]n (dmbpy = 4,4?-dimethyl-2,2?-bipyridine) has been synthesized and structurally characterized by elemental analyses, IR, UV spectra and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group C2/c with a = 17.745(4), b = 10.326(2), c = 7.3382(15) ?, β = 106.85(3)o, V = 1286.9(4) ?3, Z = 4, C12H12N2Cl2Cd, Mr = 367.54, Dc = 1.897 g/cm3, F(000) = 720, λ(MoK() = 0.71073 ?, ( = 2.089 mm-1, R = 0.0368 and wR = 0.1048 for 1041 observed reflections (I > 2σ(I)). Cadmium(II) adopts a distorted octahedral coordination geometry and adjacent coordination chains are intercalated in a zipper-like fashion into 2D layers through the π-π stacking interactions between dmbpy. Fluorescent analyses show that it exhibits intense blue photoluminescence in both DMF and DMSO solutions at room temperature.     

Catena-dichloro（4,4＇-dimethyl-2,2＇-bipyridine） Cadmium（Ⅱ）, a New One-dimensional Chain with Blue Fluorescent Emission

A new μ-chloro-bridged one-dimensional coordination polymer [Cd（dmbpy）Cl2]a （dmbpy = 4,4＇-dimethyl-2,2＇-bipyridine） has been synthesized and structurally characterized by elemental analyses, IR, UV spectra and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group C2/c with a = 17.745（4）, b = 10.326（2）, c = 7.3382（15）A, β = 106.85（3）°, V = 1286.9（4）A^3, Z = 4, C12H12N2Cl2Cd, Mr = 367.54, Dc = 1.897 g/cm^3, F（000） = 720, 2（MoKα） = 0.71073 A,μ= 2.089 mm^-1, R = 0.0368 and wR = 0.1048 for 1041 observed reflections （I 〉 2σ（I））. Cadmium（Ⅱ） adopts a distorted octahedral coordination geometry and adjacent coordination chains are intercalated in a zipper-like fashion into 2D layers through the π-π stacking interactions between dmbpy. Fluorescent analyses show that it exhibits intense blue photoluminescence in both DMF and DMSO solutions at room temperature.     

Synthesis,Crystal Structure and Magnetic Properties of a Co(Ⅱ) Complex Containing 2′-(l′-Methyl)benzimidazolyl-substituted Nitronyl Nitroxide

A new complex [Co(NIT-1′-MeBzIm)2Cl2](NIT-1′-MeBzIm = 2-{2′-[(l′-methyl)-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data:C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074(3),b = 21.350(3),c = 11.6962(19),β = 108.879(2)°,V = 4034.3(11)3,Dc = 1.160 g/cm3,μ(MoKα) = 0.597 mm-1,F(000) = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I > 2σ(I).X-ray analysis reveals that the Co(Ⅱ) ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co(Ⅱ) ion and the radicals(J =-52.88 cm-1).     

Hydrothermal Synthesis and Crystal Structure of a One-dimensional Cadmium（Ⅱ） Complex

A metal-organic coordination polymer [Cd2(cbba)4(bix)2] n·nH2O (Hcbba=2-(4′-chlorine-benzoyl)-benzoic acid, bix=1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Colorless crystals crystallize in the triclinic system, space group Pī with a=12.9891(15), b=15.3211(19), c=21.154(3), α=108.476(3), β=90.148(2), γ=105.429(3)°, V=3831.5(8)3 , C84H60Cd2Cl4N8O13 , Mr=1756.00, Dc=1.522g/cm3 , F(000)=1776, Z=2, μ(MoKα)=0.765 mm-1 , the final R=0.0724 and wR=0.1208 for 6916 observed reflections (I > 2σ(I)). The structure of 1 exhibits a one-dimensional infinite chain-like structure.     

Hydrothermal Syntheses and Crystal Structures of Two Complexes with 3,5- Dinitrosalicylate and 2,2′-Bipyridine Ligands

The two title complexes,[Cd{3,5-(NO2)2sal}(2,2′-bipy)]n 1 and [Mn{3,5-(NO2)2sal}(2,2′-bipy)]n 2 (3,5-(NO2)2sal=3,5-dinitrosalicylate,2,2′-bipy=2,2′-bipyridine),were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic,space group P1,a=5.581(4),b=12.071(8),c=12.88(1),α=92.10(3),β=96.73(3),γ =102.02(2)°,C17H10N4O7Cd,Mr=494.69,V=841(1)3,Z=2,Dc=1.954 g/cm3,F(000)=488,μ =1.353 mm-1,R=0.0248 and wR=0.0761. Complex 2 crystallizes in monoclinic with space group P21/c,a=8.604(3),b=23.88(1),c=8.894(3),β=102.45(1)°,C17H10N4O7Mn,Mr=437.23,V= 1785(1) 3,Z=4,Dc=1.627 g/cm3,F(000)=884,μ=0.791 mm-1,R=0.0471 and wR=0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units (Cd2O2) and eight-membered ring units (CdOCO)2. Compound 2 displays a linear 1D chain through Mn(Ⅱ) atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472(2). The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.     

Syntheses and Crystal Structures of Two Cadmium(Ⅱ) Compounds Linked by N,N-Bis(3-pyridylmethyl)amine

Two cadmium(Ⅱ) compounds linked by a flexible dipyridyl ligand {[Cd2(Hbpma) Cl5(H2O)]·2H2O}n 1 and [Cd(Hbpma)Cl(H2O)2]2·2SO4·3H2O 2 (bpma = N,N-bis(3-pyridylmethyl)amine) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P with a = 9.5612(6), b = 11.3401(7), c = 11.5069(12), α = 112.8540(10), β = 106.5330(10), γ = 101.6680(10)°, V = 1030.77(14)3, C12H20Cd2Cl5N3O3, Mr = 656.36, Z = 2, Dc = 2.115 g/cm3, μ(MoKα) = 2.727 mm-1, F(000) = 636, S = 1.059, the final R = 0.0319 and wR = 0.0822 for 3443 observed reflections (I > 2σ(I)). For complex 2, it belongs to triclinic, space group P with a = 10.9487(4), b = 11.4197(4), c = 15.4288(5), α = 94.7470(10), β = 104.1000(10), γ = 104.42°, V = 1790.76(11)3, C24H42Cd2Cl2N6O15S2, Mr = 1014.46, Z = 2, Dc = 1.881 g/cm3, μ(MoKα) = 1.529 mm-1, F(000) = 1020, S = 1.050, the final R = 0.0178 and wR = 0.0451 for 6026 observed reflections (I > 2σ(I)). Complex 1 is found to have tetranuclear Cd(Ⅱ) clusters which are bridged by the protonated bpma ligands leading to one-dimensional coordination polymers, whereas complex 2 consists of binuclear Cd(Ⅱ) structures linked by the protonated bpma ligands. Both complexes are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions.     

A New 3D Supramolecular Network Formed by [Zn_3（2,6-Pyridinedicarboxylate）_3Cl_4]~（4-）and 4-Carboxypyridinium

A new compound [Zn3(C7NO4H3)3Cl4]·[C6NO2H6]4·4H2O (I) has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018(14),b=12.6902(10),c=25.1170(2),β=90.54°,V=5387.0(8)3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F(000)=2840,μ(MoKa)=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections (I 2σ(I)).Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.     

Hydrothermal Synthesis and Crystal Structure of a 2D Zinc（Ⅱ） Coordination Polymer with 5-Hydroxynicotinic Acid

The title compound,[Zn(5-hydroxynicotinate) 2 2H 2 O] n,has been synthesized by reacting zinc sulfate vitriol with 5-hydroxynicotinic acid under hydrothermal conditions,and its structure was determined by X-ray crystallography with the following data:monoclinic,space group C2/c,C 12 H 12 N 2 O 8 Zn,M r=377.61,a=10.223(3),b=10.319(3),c=13.613(4),β=105.922(6)°,Z=4,V=1380.9(8)3,F(000)=768,D c=1.816 g/cm 3,μ(MoKα)=1.826 mm-1,the final R=0.0401 and wR=0.1380 for 1157 observed reflections (I > 2σ(I)).In the structure of the title compound,the Zn II ion located in an inversion center lies in a distorted tetrahedral environment at a N 2 O 2 coordination mode,and the 5-hydroxynicotinic acid ligand links symmetry-related Zn II ions at a μ 2-N,O bridging way forming a two-dimensional covalent structure.In the crystal,solvent water molecules form intermolecular O-H O hydrogen bonds and pyridine rings of adjacent layers form π-π stacking (3.346),which connect adjacent two-dimensional sheets into a three-dimensional supramolecular network.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Nickel(Ⅱ) Complex with 2-Pyridinecarboxyic Acid and 4,4′-Bipyridine Ligands

A new metal-organic coordination polymer [Ni[(2-pya)2(4,4′-bipy)]n·6nH2O (2-pya = 2-pyridinecarboxylic acid, 4,4′-bipy = 4,4′-pyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.5642(19), c = 10.7118(18), V = 5453.8(11) 3, C22H28N4NiO10, Mr = 567.19, Dc = 1.382 g/cm3, μ(MoKα) = 0.769 mm-1, F(000) = 2368, Z = 8, the final R = 0.0572 and wR = 0.1254 for 1401 observed reflections (I > 2σ(I)). It exhibits a one-dimensional chain-like structure by mixed ligands of 2-pyridinedicarboxylic acid and 4,4′-pyridine.     

Synthesis,Crystal Structure and Photoluminescence of [Gd(C_6NO_2H_5)_3-(H_2O)_2]_(2n)·(nH_5O_2)(nHgCl_5)(2nHgCl_4)·(2nH_2O)

A heterometallic 4f-5d inorganic-organic metal-isonicotinato hybrid Gd(C6NO2H5)3-(H2O)22n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O) 1 has been synthesized via hydrothermal reaction and structurally characterized.Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell:a=24.234(8)=b=20.816(7)=c=15.333(3)=β=128.091(8)°=V=6088(3)3=C36H47Cl13Gd2Hg3N6O20=Mr=2260.92=Dc=2.467 g/cm3=S=0.896=μ(MoKα)=10.331 mm-1=F(000)=4216=R=0.0344 and wR=0.0629.The crystal structure analysis reveals that the title complex is characteristic of a one-dimensional chain-like structure.Photoluminescent investigation reveals that the title complex displays a broad and intense emission in the green region.     

A New Cadmium（Ⅱ） Coordination Polymer Incorporating a 3D Framework with 1D Channels Bridged by Flexible Cyclohexane-1,2,4,5-tetracarboxylate Ligand

The hydrothermal reaction of Cd(OAc)2·2H2O, 4,4'-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid (H4L) yields a three-dimensional (3D) coordination porous framework [Cd2LI(4,4'-bpy)1.5(H2O)2]n·2nH2O, which was characterized by single-crystal X-ray diffraction (MoKα radiation, λ = 0.71073), elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951(3), b = 11.6618(12), c = 20.046(2) , β = 114.863(2)o, V = 5504.4(10) 3, Z = 8, Dc = 1.900 g/cm3, Mr = 787.30, μ = 1.615 mm-1, F(000) = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4'-bpy ligands. The 4,4'-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I (e,a,a,e) conformation and acts as a pentadentate ligand to connect five Cd(Ⅱ) atoms via the carboxylate groups in different coordination modes.     

Synthesis and Crystal Structure of a Zinc（Ⅱ）Complex with 2,2＇-Diphenic Acid and Benzimidazole Ligands

A new complex [Zn1.5(dpa)1.5(bim)]2n(dpa = 2,2-diphenic acid,bim = benzimida-zole)1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,fluorescence spectrum and single-crystal X-ray diffraction.The complex crystallizes in monoclinic,space group C2/c with a = 18.773(8),b = 16.560(7),c = 16.417(9),β = 94.737(9)o,V = 5086(4)3,C56H36N4O12Zn3,Mr = 1153.00,Dc = 1.506 g/cm3,μ(MoKα)= 1.472 mm1,F(000)= 2344,Z = 4,the final R = 0.0573 and wR = 0.1164 for 2968 observed reflections(I > 2σ(I)).It exhibits a one-dimensional chain-like structure and shows luminescent property in the blue region.     

Synthesis and Crystal Structure Analysis of 5′-O-Tosyl-2,3′-anhydrothymidine

In this paper=5′-O-tosyl-2,3′-anhydrothymidine has been synthesized and its crystal structure was analyzed. The crystal belongs to the triclinic system=space group P1=with a=5.397(2)=b=6.1886(18)=c=3.507(5) =α =87.74(2)=β =89.84(4)=γ =73.79(2)°=C17H18N2O6S=Mr=378.39=Z=1=V=432.8(3)3=Dc=1.452 g/cm3=F(000)=198 and Flack =-0.11(14). No intermolecular hydrogen bonds exist in the crystal=and the angle between benzene ring and pyrimidine planes is 32.23°.     

Hydrothermal Synthesis,Structure and Photo-luminescence of a 2D Lead(Ⅱ) Coordination Polymer with (4,_6~3)Topology Based on Pb and 1,2,3,4-Butanetetracarboxylate Nodes

A lead(II) coordination polymer,{[Pb2(butca)(H2O)2](H2O)2}n (1),has been synthe-sized by the hydrothermal reaction of Pb(OH)2 and 1,2,3,4-butanetetracarboxylic acid (H4butca) at 160 °C.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group P21/c with a=7.616(5),b=7.584(4),c=12.314(7),β=105.595(12)o,V=685.0(7)3,Z=4,C8H14O12Pb2,Mr=716.57,Dc=3.474 g/cm3,μ=24.610 mm-1,F(000)=644,the final R=0.0381 and wR=0.1176 for 1465 observed reflections with I 2σ(I).The complex presents a 2D-layered structure featuring two different types of rings,and has a (4,36)topology based on Pb and butca4-nodes.In solid state,complex 1 shows photoluminescence with the maximum emission intensity at 468 nm under 286 nm excitation.     

Hydrothermal Synthesis and Crystal Structure of a Manganese(Ⅱ) Polymer with a Two-dimensional Network Structure:[Mn(pzdc)(phen)]_n·nH_2O

A metal-organic coordination compound formulated as [Mn(pzdc)(phen)]n·nH2O 1 (H2pzdc=pyrazine-2,3-dicarboxylic acid,phen=1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the monoclinic system,space group P21/n with a= 11.7689(18),b=11.7458(18),c=13.360(2),β=110.341(2)o,V=1731.7(5)3,C18H12MnN4O5,Mr=419.26,Dc=1.608 g/cm3,μ(MoKα)=0.803 mm-1,F(000)=852,Z=4,the final R=0.0323 and wR=0.0823 for 2831 observed reflections (I 2σ(I)).It exhibits an interesting two-dimen-sional network structure.     

Synthesis,Crystal Structure,and Photoluminescent and Semiconductive Properties of [La(C_6NO_2H_5)_3-(H_2O)_2]_(2n)·(nH_5O_2)(nHgCl_5)(2nHgCl_4)·(2nH_2O)

A new heterometallic 4f-5d inorganic-organic metal-isonicotinic acid complex [La(C6NO2H5)3(H2O)2]2n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O) 1 has been synthesized via hydro-thermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell:a =24.140(7),b=20.884(7),c=15.462(2),β=127.46(1)°,V=6187(3)3,C36H47Cl13Hg3La2N6O20,Mr=2224.24,Dc=2.388 g/cm3,Z=4,T=293(2) K,μ(MoKα)=9.401 mm-1,F(000)=4160 and R/wR=0.0376/0.0636 for 4130 observed reflections (I > 2σ(I)) and 5617 unique reflections. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in violet and orange regions. The luminescence spectra show stronger orange emission than violet emission. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap of 3.41 eV.     

Synthesis and Crystal Structure of a Zinc(II) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4′-chlorine-ben-zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821(11), b = 18.3140(17), c = 30.961(3), V = 6850.7(11)3, C80H48Cl4N4O12Zn2, Mr = 1529.76, Dc = 1.483 g/cm3, μ(MoKα) = 0.925 mm?1, F(000) = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections (I > 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.     

Synthesis and Crystal Structure of a New Complex [Cd（C20H14N4）2Cl2]

The title compound [Cd(C20H14N4)2Cl2] 1 was synthesized via the hydrothermal reaction of CdCl2·7H2O and NaOH with 1,3-bis(benzimidazol-2-yl)benzene (BMB), and characterized by elemental analysis and infrared spectra. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 21.021(6), b = 9.489(3), c = 18.302(6), β = 108.686(6)o, V = 3458.2(19)3, Z = 4, C40H28CdN8Cl2, Mr = 804.01, Dc = 1.544 g/cm3, F(000) = 1624 and μ(MoKα) = 0.829 mm-1. The final R = 0.0306 and wR = 0.0779 for 3334 observed reflections with I > 2σ(I) and R = 0.0796 and wR = 0.0360 for all data. The cadmium atom is four-coordinated by the BMB ligands and Cl atom with a tetrahedral geometry. The extensive N-H···N hydrogen bonding interactions are observed in the structure, which further extend the [Cd(C20H14N4)2Cl2] units into a 1D structure. The thermogravimetric analysis measurement showed that compound 1 has thermal stability as no strictly clean weight loss step occurred below 425 ℃.     

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.     

Supramolecular Formation via Hydrogen Bonding in Copper and Nickel Complexes with 2-Hydroxynicotinic Acid

Two complexes,Cu(HnicO)2 1 and Ni(HnicO)2(H2O)2 2 (H2nicO=2-hydroxy-nicolinic acid),were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in monoclinic,space group P21/n,with a=8.314(7),b=6.275(4),c=11.283(7),β =98.32(3)°,V=582.5(7)3,Z=2,Mr=339.74,Dc=1.937 g/cm3,F(000)=342,μ=1.908 mm-1,S =1.097,the final R=0.0284 and wR=0.0781 for 1177 observed reflections with I > 2σ(I). Complex 2 crystallizes in monoclinic,space group P21/c,with a=7.438(5),b=12.22(1),c=7.537(5),β=100.07(3)°,V=674.3(8)3,Z=2,Mr=370.95,Dc=1.827 g/cm3,F(000)=380,μ =1.487 mm-1,S=1.041,the final R=0.0335 and wR=0.0779 for 1202 observed reflections with I > 2σ(I). There are extended 3D framework structures in complexes 1 and 2 due to the N–H…O and C–H…O hydrogen bonds. The copper atom in 1 has square planar coordination,while the nickel atom in 2 adopts octahedral coordination geometry. The TG curve shows that complex 2 is stable in solid state to 150 ℃.