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.     

Hydrothermal Synthesis,Crystal Structure and Luminescent Property of a Cd(Ⅱ) Compound with(4,6)-Connected Topology

A new Cd(Ⅱ) coordination polymer, namely {Cd_2(L)(biimpy)(H_2O)}_n(1, H4 L = 3-(3?,5?-dicarboxylphenoxy)phthalic acid, biimpy = 2,6-bis(1-imdazoly)pyridine), has been successfully synthesized via the hydrothermal reactions of Cd(Ⅱ) ions, H_4L and biimpy. The crystal structure is of triclinic, space group P1 with a = 7.7874(5), b = 9.9716(5), c = 18.5278(6) ?, α = 91.327(4), β = 96.689(4), γ = 111.896(5)o, V = 1322.39(12) ?~3, C_(27)H_(17)Cd_2N_5O_(10), M_r = 796.26, Z = 2,D_c = 2.000 g/cm~3, F(000) = 780, μ = 1.679 mm~(-1), R = 0.0345 and wR = 0.0767 for 3890 observed reflections(I 2s(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional(3D) framework based on two different dinuclear [Cd_2(COO)_2] building subunits, and topological analysis shows that it can be simplified into a binodal(4,6)-connected topological network with the point symbol of {3.4~2.5~2.6}{3~2.4~2.5~2.6~4.7~4.8}. Moreover, the thermal stability and luminescent property of compound 1 were also studied.     

A Luminescent Cd(Ⅱ) Coordination Polymer Constructed from Isophthalic Acid and 1,3-Bis-(4-pyridyl)propane

A new coordination complex [Cd2(ip)2(bpp)]n(1, H2 ip = isophthalic acid, bpp = 1,3-bis-(4-pyridyl) propane) has been synthesized and structurally characterized. Crystal data for the title complex are as follows: triclinic system, space group P1 with a = 9.6724(6), b = 10.2243(6), c = 14.8205(9) ?, α = 88.927(5), β = 71.664(6), γ = 75.767(5)°, V = 1345.79(14) ?3, Mr = 751.29, Z = 2, F(000) = 740, Dc = 1.854 g/cm3, μ(Mo Kα) = 1.636 mm-1, R = 0.0259 and w R = 0.0623 for 4754 observed reflections with I 2σ(I). X-ray structure analysis reveals that complex 1 holds a 3D architecture based on α-Po primitive cubic units with the [Cd4(COO)8] units treated as 6-connected nodes. Solid-state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.     

Crystal Structure and Luminescent Properties of a Zn(Ⅱ) Coordination Polymer Assembled by Mixed-ligand

A Zn(Ⅱ) coordination polymer [Zn(NIP)(3,3'-bpt)]·H2O(1, NIP = 5-nitroisophthalate, 3,3'-bpt = 1H-3,5-bis(3-pyridyl)-1,2,4-triazolate) has been synthesized by the hydrothermal reaction at 140 ℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2 NIP and two nitrogen atoms from two 3,3'-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.     

Synthesis,Crystal Structure and Photoluminescent Property of a New Ca(Ⅱ) Compound Constructed from 5-Oxyacetateisophthalic Acid

A new coordination polymer, namely [Ca(HOABDC)]n(1, H3 OABDC = 5-oxyacetateisophthalic acid), has been synthesized through hydrothermal reactions of Ca(NO3)2 and H3 OABDC. The title compound crystallizes in monoclinic, space group P21/c with a = 4.3043(2), b = 21.4959(11), c = 10.7450(6) A, β = 91.411(5)o, V = 993.88(9)A3, C10H6O7 Ca, Mr = 278.23, Z = 4, Dc = 1.859 g/cm3, F(000) = 560, μ = 0.659 mm-1, the final R = 0.0328 and wR = 0.0670 for 1469 observed reflections(I 2A(I)). Single-crystal X-ray structural analysis reveals that compound 1 features 1D Ca(Ⅱ)-carboxylate chain-shaped subunits, which are further connected together via HOABDC2- ligands into a 3D(6,6)-connected nia-type hybrid framework. Moreover, the luminescent property and thermal stability of 1 were also investigated.     

Synthesis, Crystal Structure and Luminescent Properties of a Novel 2D Sheet Cd(Ⅱ) Coordination Polymer [Cd(Cpna)(Py)]n

A coordination polymer, [Cd(cpna)(py)]n(H2cpna = 5-(2-carboxylphenyl) nicotic acid, py = pyridine) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectra and single-crystal X-ray diffraction. Colorless crystals crystallize in the monoclinic system, space group P21/c with a = 8.589(2), b = 13.047(3), c = 14.940(4) , β = 96.001(2)°, V = 1664.9(7) 3 , C18H12CdN2O4 , Mr = 432.70, Dc = 1.726 g/cm 3 , F(000) = 856, Z = 4, μ(MoKα) = 1.337 mm -1 , the final R = 0.0396 and wR = 0.0891 for 2422 observed reflections (I > 2σ(I)). Complex 1 exhibits a two-dimensional (2D) sheet structure, which further builds a three-dimensional (3D) supramolecular architecture via C-H···O hydrogen-bonding interactions.     

Synthesis,Crystal Structure and Luminescent Properties of a Novel 1D Zigzag Chain Barium(Ⅱ) Coordination Polymer

A new coordination polymer {[Ba(L)(H2O)5]·H2O}n(1, H2 L = 3,3'-((((ethane-1,2-diylbis(oxy))-bis(2,1-phenylene))bis(methylene))bis(oxy))dibenzoic acid) has been synthesized under evaporation process and characterized by elemental analysis, IR spectra, TG analysis,fluorescence spectrum, powder X-ray diffraction analysis and single-crystal X-ray diffraction.Complex 1 crystallizes in the monoclinic system, space group P21/c, with a = 20.918(5), b =7.4539(2), c = 20.168(5) A, β = 95.486(2)o, V = 3130.1(1) A3, Z = 4, C30H34 Ba O14, Mr = 755.91, Dc =1.604 g/cm3, F(000) = 1528, μ = 1.34 mm-1, the final R = 0.0404 and w R = 0.0676 for all data.Single-crystal X-ray structural reveals that the Ba(II) ion adopts a nine-coordinated distorted tricapped trigonal prism coordination geometry. Adjacent Ba(II) ions are linked by one μ2-L2- anion and two(μ2-H2O) water molecules to generate an infinite 1D zigzag chain structure. Then these chains are further linked into a 2D layer supramolecular architecture through O–H···O hydrogen bonds. Luminescent property and thermal stability of complex 1 were investigated.     

Syntheses,Crystal Structures,Magnetic and Luminescent Properties of Ni(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ) Coordination Compounds Constructed from 5-Fluoronicotinic Acid

Five coordination compounds, namely [Ni_2(5-Fnic)_2(H_2 O)_4](1), [Ni(5-Fnic)(μ-5-Fnic)(H_2 biim)]n(2), {[Cd((μ-5-Fnic)2(H2 O)2]×4,4'-bipy}n(3), [Pb_2(μ-5-Fnic)_2(μ3-5-Fnic)_2(H_2 O)_2]n(4), and [Pb(5-Fnic)_2(4,4'-bipy)(H_2 O)](5), have been constructed hydrothermally using 5-FnicH(5-FnicH = 5-fluoronicotinic acid), H_2 biim(H_2 biim = 2,2'-biimidazole), 4,4'-bipy(4,4'-bipy = 4,4'-bipyridine), NiCl_2×6 H_2 O, CdCl_2×H_2 O and PbCl_2. 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. Structures of 1～5 range from discrete 0 D monomers(1 and 5) to 1 D coordination polymers(2 and 4) and 2 D metal-organic network(3). A broad structural diversity of 1～5 is guided by the type of the metal(Ⅱ) node and the introduction of auxiliary ligands. The magnetic(for 2) and luminescent(for 3～5) properties were also investigated and discussed.     

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.     

Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis

Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C-H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.     

Synthesis,Crystal Structure and Physical Properties of a Novel Cadmium(Ⅱ) Supramolecular 3D Framework

A new inorganic-organic hybrid cadmium(Ⅱ) complex [Cd2(H1/2C4BIm)2(CH3COO)]nhas been prepared by a hydrothermal reaction,and characterized by fluorescence,IR,TGA,and single-crystal X-ray diffraction analysis.In its crystal structure,there are two kinds of coordinating forms for those Cd(Ⅱ) ions.One is that the Cd(Ⅱ) ion is coordinated by one carboxylate oxygen atom from one acetate oxygen ligand and three benzimidazole nitrogen atoms from three 2,2’-(1,4-butanediyl)bis(1H-benzimidazole)(H2C4BIm) ligands,and the other is that the Cd(Ⅱ) ion is coordinated by four benzimidazole nitrogen atoms from four H2C4 BIm ligands to furnish two distorted tetrahedral coordination geometries.It exhibits a beautiful structure for a 2D layer and a 3D network,with its four-connecting nodes provided by the H2C4 BIm ligands.Furthermore,this complex shows intense luminescent property at room temperature.In [Cd2(H2C2BIm)2(C9H6O4)2]n,the H2C2 BIm ligand lost the role as a bridging ligand because of the shorter alkyl chain compared with that of H2C4 BIm ligand.     

Synthesis and Crystal Structure of a Copper(Ⅱ) Compound Constructed by N-(4,6-Dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea

A copper(Ⅱ ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dime- thoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385(7), c = 22.0008(18) , β = 108.077(2)o, V = 3104.3(5)3, Dc = 1.627 g/cm3, Z = 4, C20H28CuN10O14S2, Mr = 760.18, μ(MoKα) = 0.920 mm–1, F(000) = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections (I > 2σ(I)). X-ray diffraction shows the existence of weak complementary intramolecular N–H…O (DA) hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu(II) ion, intermolecular C–H…O hydrogen bonds and weak π…π stacking interactions, leading to the formation of a multi-dimen- sional supramolecular network.     

Synthesis, Crystal Structure and Luminescent Properties of a Novel Zinc(Ⅱ) Complex of N-Acetyl-L-glutamic Acid and Imidazole Ligands

A novel complex (Zn(Im)2(A-glu)·0.5H2O (Im = imidazole, A-glu = N-acetyl- L-glutamic acid) has been synthesized from the reaction of A-glu with Zn(CH3COO)2(2H2O in the presence of Im at 65 ℃, and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group P43212 with a = b = 8.9078(6), c = 43.458(6) (A), C26H36N10O11Zn2, Mr = 795.39, V = 3448.3(6) (A)3, Dc = 1.532 g/cm3, Z = 4, μ(MoK() = 1.461 mm(1, F(000) = 1640, the final R = 0.0453 and wR = 0.0992. X-ray analysis reveals that the crystal structure is constructed by mixed ligands. A-glu adopts the bis-monodentate coordination mode linking two adjacent metal ions to form a one-dimensional chain. Zinc(Ⅱ) ions are four-coordinated with a distorted tetrahedral geometry. Luminescent properties of the complex have been inves- tigated.     

Synthesis,Crystal Structure and Luminescent Properties of a Nd（Ⅲ） Complex Constructed from 2-Pyridyl-4,5-imidazoledicarboxylic Acid

A new Nd(Ⅲ) coordination polymer [Nd(pidc)(H2O)4]·pidc-·7H2O(1,pidc2-= 2-py-ridyl-4,5-imidazoledicarboxylate) has been synthesized by solvothermal reaction at 120 ℃ and structurally characterized.The complex belongs to triclinic,space group P with a = 9.022(2),b = 13.731(3),c = 13.782(3) ,α = 70.87(3),β = 71.71(3),γ = 71.71(3),V = 1488.6(7) 3,Z = 2,Dc = 1.798 g/cm3,S = 1.04,μ = 1.839 mm-1,F(000) = 814,Mr = 805.76,Rint = 0.081 and wR = 0.1644 for 5242 observed reflections(I > 2(I)).Each Nd3+ ion is nine-coordinated by five O atoms from three pidc ligands,and four O atoms from lattice water molecules.Each pidc is coordinated to three Nd3+ ions with a μ3-κO:κO':κO",κO'"-μ2 coordination mode into 1D chains,which can be further built into a 3D framework through intermolecular N-H···O and O-H···O hydrogen bonds.Photolu-minescent studies have shown that 1 exhibits emission at 439 nm(λex = 395 nm).     

Synthesis and Crystal Structure of a Novel Terpyridine-based Cd(Ⅱ) Complex

A novel terpyridine-based complex CdL'S2 (L'= oxide of L; L = 10-hexyl-3-(2,6-di(pyridine-2-yl)pyridine-4-yl)-10H-phenothiazine) has been solvothermally synthesized and characterized by FT-IR spectroscopy, elemental analysis, 1 H NMR and X-ray crystallography. The sulfur of phenothiazine moiety was oxidized when the crystal is formed. The complex C36H37CdN5O2S3 crystallizes in triclinic, space group P1 with a = 9.4452(9), b = 13.0181(14), c = 14.6721(18), α = 73.872(1), β = 81.531(1), γ = 87.547(2)°, V = 1714.2(3)3 , Mr = 780.29, Dc = 1.512 g·cm-3 , μ = 0.861 mm-1 , F(000) = 800, Z = 2, the final R = 0.0456 and wR = 0.1059 for Ⅰ > 2σ(Ⅰ). The Cd(Ⅱ) is coordinated by two terminal sulfur ions and three pyridyl nitrogen atoms in a distorted trigonal bipyramidal geometry. Universal hydrogen bonds between the neighboring molecules have generated a supramolecular arrangement which contributes to the stability of the title complex. Fluorescence property and thermogravimetry of the complex have also been investigated and discussed.     

Synthesis,Crystal Structure and Properties of a 3-Fold Interpenetrating 3D Cd(Ⅱ) Complex Derived from 4-(2-Methyl-1H-imidazol-1-yl)benzoic Acid

A new Cd~Ⅱ coordination complex,namely [Cd(iba)_2]_n(1),was prepared by the hydrothermal reaction of Cd(NO_3)_2·4H_2O with 4-imidazol-1-yl-benzoic acid(Hiba). Single-crystal X-ray diffraction analysis shows that compound 1 crystallizes in monoclinic system,space group Cc with a = 11.403(4),b = 30.480(9),c = 7.732(3) ?,β = 130.189(4)o,V = 2503.0(1) ?~3,Z = 4,C_(22)H_(18)CdN_4O_4,Mr = 514.80,Dc = 1.666 g/cm~3,F(000) = 1032 and μ(Mo Kα) = 1.101 mm-1. The final R and wR are 0.0573 and 0.1823 for 4421 observed reflections with I 2σ(I). Each iba-ligand coordinates in a bidentate fashion,connecting the Cd(Ⅱ) atoms to form a 2D wave-shape layer structure,which can be simplified as a four-connected topological net. Interestingly,the 2D layers are further extended into a 3-fold interpenetrating 3D architecture. Compound 1 displays an emissive maximum at 455 nm in the solid state at room temperature and a response of the second harmonic generation(SHG) activity is approximately 0.8 times that of KDP.     

Synthesis and Crystal Structure of a New 2D O-bridged Copper(Ⅱ) Coordination Polymer Constructed from Sulfonate-derived Schiff Base

A new chain-like coordination polymer, namely, [CuL ]n(1, Na2 L = 2-[(2-hydroxybenzylidene)-amino]-benzenesulfonic acid sodium salt), has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a = 9.2296(16), b = 10.4754(18), c = 12.200(2) A, β =102.392(2)°, V = 1152.0(3) A3, C13H9 CuN O4S, Mr = 338.83, Dc = 1.953 g/cm3, Z = 4, F(000) = 684,μ = 2.089 mm-1, the final R = 0.0376 and w R = 0.0956. X-ray diffraction analyses indicate that 1displays a square-pyramidal metal center with NO4 donor sets. The sulfonate-derived Schiff base serves as a common N,O,O′-tridentate and a unique O-bridged ligand connecting the metals.Dinuclear copper complexes serve as secondary building blocks(SBUs) to construct an unusual2 D coordination network. In the crystal, the components form a stable 3D supramolecular architecture by C–H···O interactions and π-stacking.     

Syntheses,Crystal Structures and Luminescent and Magnetic Properties of Cerium(Ⅲ) and Zinc(Ⅱ) Coordination Compounds Constructed from 3,5-Dibromobenzoic Acid

Two coordination compounds, namely [Ce(3,5-Br2BC)3(3,5-HBr2BC)]n(1) and [Zn(3,5-Br2BC)2(phen)](2, 3,5-HBr2 BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline), 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 Br···Br and Br···O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C–H···O hydrogen bond, π-π stacking interactions and Br···π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.     

Hydrothermal Synthesis,Crystal Structure and Thermal Property of a Coordination Polymer Constructed by Ce(Ⅲ) and Succinate Ions

A new three-dimensional coordination polymer [Ce_2(C_4H_4O_4)_3(H_2O)_2]_n·3.2 nH_2 O, constructed by Ce(Ⅲ) ion and succinate ion and lattice water molecules has been synthesized under hydrothermal conditions. It crystallizes in triclinic system, space group P1 with a = 7.8865(6), b = 12.0260(8), c = 12.2598(9) ?, α = 112.456(2)o, β = 90.046(2)o, γ = 100.423(2)o, Mr = 722.14, V = 1053.73(13) ?~3, Z = 2, Dc = 2.276 g/cm~3, μ = 4.35/mm, F(000) = 696, GOF = 1.029, R = 0.0203 and w R = 0.0570. The asymmetric unit contains two Ce~(3+) cations and both of them are nine-coordinated and their coordination geometries can be described as two distorted monocapped square antiprisms. In the title compound, a three-dimensional coordination network with one-dimensional hexagon honeycomb-like channels along the a axis is generated. TG measurement has been carried out, and its result analysis along with the powder XRD determination indicates the residue to be CeO_2.