A New 4-Connected Ni~Ⅱ Coordination Polymer with a Novel 3D 2-Fold Interpenetrated Framework

A coordination polymer [Ni(pbc)2(H2O)]n(Hpbc = 3-pyrid-4-ylbenzoic acid) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction,IR and elemental analysis.The crystal is of monoclinic,space group C2/c with a=19.624(5),b=12.029(5),c=19.452(5),β=104.45(5)°,C24H18NiN2O5,Mr=473.11,V=4447(2)3,Dc=1.413 g/cm3,F(000)=1952,μ = 0.91 cm-1,Z = 8,the final R=0.0424 and wR=0.0871 for 3757 reflections with I2σ(I).X-ray diffraction analysis reveals that the pbc-ligands act as diconnectors to link two Ni(Ⅱ) centers and adopt two coordination modes of μ2-N,O and μ2-N,O,O to form infinite wavy nickel-carboxylate chains along the bc plane.The topological analysis of compound [Ni(pbc)2(H2O)]n reveals that it is a typical CdS framework.     

A Novel 3D Cu(Ⅱ) Coordination Polymer Containing Mixed Ligands: Synthesis,Crystal Structure and Properties

A novel compound, {[Cu2(nbdc)2(4,4'-bpy)2(H2O)2]·2H2O}n(H2nbdc = 4-nitrobenzene-1,2-dicarboxylic acid, 4,4'-bpy = 4,4'-bipyridine), was hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), and single-crystal X-ray diffraction. The complex is of orthorhombic system, space group Pbcn with a = 32.222(7), b = 7.8503(16), c = 28.389(6), V = 7181(3)3, Dc = 1.720 g/cm3, Mr = 929.74, Z = 8, F(000) = 3792, μ = 1.273 mm-1, the final R = 0.0591 and wR = 0.1378 for 4548 observed reflections with I 2σ(I). The compound exhibits a 3D self-penetrating framework with bcu net topology, in which the(46·48)-networks are joined by the H2nbdc and 4,4'-bpy linkers.     

Synthesis and Characterization of a Two-dimensional Cadmium(Ⅱ) Metal Organic Framework with Fes Topology

A new Cd(Ⅱ) coordination polymer, {[Cd(Hnbta)(L)]·H2O}n(L = 1,4-bis(5,6-dimethylbenzimidazol-1-yl)butane), H3nbta= 5-nitrobenzene-1,2,3-tricarboxylic acid), has been hydro-thermally synthesized and characterized by elemental analyses, IR, XRPD, and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 17.3056(13), b = 11.0114(9), c = 17.7484(14) A, β = 117.3640(10)o, V = 3003.7(4) A3, Z = 4, C31H31CdN5O9, Mr = 730.01, Dc = 1.614 g/cm3, μ = 0.792 mm-1 and F(000) = 1488. The cadmium(Ⅱ) ions are bridged by Hnbta2- to generate a two-dimensional metal organic framework with fes topology. In addition, the thermal stability and fluorescence properties of the complex were also studied.     

Two Amine-tethered Imidazolium NHC Ni(Ⅱ) Complexes: Synthesis,Structure and Catalytic Activity

Nickel(Ⅱ) complexes Ni(L1)2(1) and Ni(L2)2·CH3CN·H2O(2)(L1Cl = 2-(3-benzyl-2,3-dihydroimidazlo-1-yl)-N-(pyridin-2-yl)acetamide, chloride salt, L2Cl = 2-(3-naphthalene-2-ylmethyl)-2,3-dihydro-imidazlo-1-yl)-N-phenylacetamide, chloride salt) with amide-functionalized imidazolium NHC ligand were synthesized and determined by single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 9.2561(19), b = 15.138(3), c = 20.750(4) , β = 90.216(3)°, V = 2907.3(10) 3 and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Pbca with a = 15.5469(16), b = 15.3521(15), c = 31.177(3) , V = 7441.2(13) 3 and Z = 8. They are stable in the air and formed via intermolecular weak interactions, including C–H···π contacts and C–H···O hydrogen bonds. Complex 1 was applied in Suzuki coupling reaction through the investigation of reaction conditions under the optimal choice conditions: 80 ℃, K3PO4, 3% mol catalysts, 6% mol PPh3 and toluene as solvent system could afford 96% yield in 5 h.     

A Three-dimensional Zn~(Ⅱ) Based Coordination Polymer with 2-Fold Interpenetrated Topology Displaying Luminescent Property

A new coordination polymer, [Zn2(m-bix)(p-bdc)2](1), was synthesized under hydrothermal conditions by a reaction of 1,3-bis(imidazol-1-ylmethyl)benzene(m-bix), 1,3-benzenedicarboxylic acid(H2p-bdc) and Zn(NO3)2. The colorless block crystals of complex 1(C30H22N4O8Zn2) belong to the triclinic system, space group P1 with a = 10.213(2), b = 12.052(2), c= 12.392(3) A, α = 82.97(3), β = 76.04(3), γ = 78.02(3)o, V = 1443.8(5) A3, Z = 2, Dc = 1.604 g/cm-3,Mr = 697.26, F(000) = 708, R = 0.0403 and w R = 0.0907 for 4886 observed reflections(I 2σ(I)). In1, the tetrahedral ZnI I cations are linked by [p-bdc]2– anions into 2D sq1 networks, which are further connected by bix ligands forming an interesting 2-fold 4,4-connected mog-type 3D network with a point symbol of {4·64·8}2{42·62·82}. Complex 1 was characterized by elemental, IR spectroscopy,powder X-ray diffractions and thermalgravimetric analysis. In addition, complex 1 exhibits coordination induced photoluminescent property.     

Syntheses,Crystal Structures and Catalytic Properties of Copper(Ⅱ) and Cobalt(Ⅱ) Complexes Containing 5,6-Dimethylbenzimidazole

Two new complexes, [Cu(DMB)2(NAA)2](1) and [Co(DMB)2(NAA)2](2)(DMB = 5,6-dimethylbenzimidazole, HNNA = 1-naphthylacetic acid), were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA, PXRD and single-crystal X-ray diffraction analysis. The coordination geometry of the metal centers is a perfect square plane for 1 and a distorted tetrahedron for 2. In compound 1, the mononuclear units are linked by N–H···O hydrogen bonds to form a 1D chain structure, while mononuclear motifs of 2 are extended via N–H···O hydrogen bonding and π-π stacking interactions into a 2D supramolecular layer. The remarkable catalytic properties of the two complexes for the degradation of Congo red dye have been found.     

Dinuclear Copper（Ⅱ） Complex with a New Polycarboxylate Ligand：Syntheses,Characterization and Crystal Structure

A dinuclear copper(Ⅱ) complex,[Cu2(HL)2(H2O)6] 1(H3L = 2,4,6-tri(3-carboxy-phenylthio)-1,3,5-triazine),was synthesized hydrothermally and characterized by single-crystal X-ray diffraction,IR and thermal analysis.Single-crystal X-ray diffraction reveals that complex 1 is a dinuclear copper(Ⅱ) complex,which is further extended to a 3D network by weak interactions such as O…H-O hydrogen bonds and noncovalent S...S interactions.The crystal of compound 1 belongs to monoclinic,space group C2/c,with a = 50.15(2),b = 6.789(3),c =15.667(8) ,β = 90.588(9)o,V = 5334(4) 3,Z = 4,C48H38Cu2N6O18S6,Mr = 1306.28,Dc = 1.627 g/cm3,F(000) = 2664,Rint = 0.0631,T = 293(2) K,μ = 1.112 mm-1,the final R = 0.0661 and wR = 0.1850 for 3782 observed reflections with I > 2σ(I).     

A Three-dimensional Cd(Ⅱ) Coordination Polymer with Unique 8-Connected LOMFOI Topology Based on Mixed Flexible N/O Ligands

A new metal-organic framework,{[Cd(DPA)(OBA)]·(H2O)}n(1,DPA = 4,4-dipyridylamine,H2OBA = 4,4-oxybisbenzoic acid),has been synthesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.Single-crystal X-ray analysis shows that it is a 3-D framework.Complex 1 crystallizes in monoclinic,space group C2/c with a = 21.699(7),b = 12.192(4),c = 17.566(5) ,β = 105.254(5)°,V = 4483.43 3,Z = 8,Dc = 1.653 g/cm3,μ = 1.021 mm-1,F(000) = 2240,the final R = 0.0307,wR = 0.0867(I 2σ(I)).Complex 1 exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424·64}.Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400 ℃.     

Synthesis,Crystal Structure,DNA Binding and Catalytic Activities of a New Unsymmetrical Macrocyclic Dinuclear Zn(Ⅱ) Complex

An unsymmetrical macrocyclic dinuclear Zn(II) complex, [Zn2(H0.5L)(OAc)](ClO4)1.5(1, H2 L is the condensation product between 2, 6-diformyl-4-methylphenol and diethylenetriamine), was obtained and characterized by IR spectrum, elemental analysis and X-ray single-crystal diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 16.784(2), b = 19.474(3), c = 10.3364(13), β = 92.923(2)°, V = 3374.1(7) 3, Z = 4, Dc = 1.672 g/cm3, F(000) = 1740, μ = 1.651 mm-1, the R = 0.0609 and wR = 0.1696 for 4745 observed reflections(I 2σ(I)). The interactions of the complex with DNA have been measured by electrochemical studies, UV spectroscopy and viscosity experiment. The interactions of the complex with calf thymus DNA were studied by UV-vis spectra and the binding constant is 1.58 × 104 mol·L-1. The phosphate hydrolysis catalyzed by the complex was investigated using 4-nitrophenyl phosphate(NPP) as the substrate; the observed first order rate constant value is 3.0 × 10–4 s-1.     

A Novel Two-dimensional Lead(Ⅱ) Coordination Polymer Based on Dinuclear Lead(Ⅱ) Unit Containing(5-Chloro-quinolin-8-yloxy) Acetate

A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603(7), b = 8.6907(4), c = 8.4745(3), β = 101.1110(11)°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25(9)3, Z = 4, Dc = 2.628 g/cm3, F(000) = 880, μ = 14.367 mm-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead(II) cation, one(5-chloro-quinolin-8-yloxy)acetate(L) ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit(SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H···Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1). The fluorescence emission peak of complex 1 appears near 407 nm.     

A 3D Ba(Ⅱ) Inorganic-organic Hybrid Framework Based on 1,3,5-Benzenetricarboxylic Acid Ligand: Synthesis and Characterization

A three-dimensional(3D) barium complex with 1,3,5-benzenetricarboxylic acid(H3BTC), {[Ba1.5(BTC)(H2O)]·(H2O)}n(1), was synthesized in DMF/EtOH/H2 O mixed solution under solvothermal conditions, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses, and photoluminescence measurement. In complex 1, the 2D I2O0 type inorganic layer is constructed by {Ba1O10} and {Ba2O9} polyhedra. Moreover, the solid-state fluorescence measurement reveals a fluorescence emission band at 465 nm under 344 nm excitation, assigned to a charge-transfer transition.     

Synthesis,Crystal Structure,and Topology Analysis of One Novel Interpenetrated 2D Cobalt Coordination Polymer, {[Co(HTCB)(4,4'-btb)]·H_2O}_n

One novel cobalt coordination polymer, {[Co(HTCB)(4,4'-btb)]·H2O}n(1, H3TCB= 1,3,5-tris(4-carboxyphenyl)benzene, 4,4'-btb = 4,4'-bis(1,2,4-triazol-3-yl)biphenyl), has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql [Co(HTCB)(4,4'-btb)] sheet based on the 1D [Co(HTCB)]n chains and1 D [Co(4,4'-btb)]n chains. The crystal of 1 crystallizes in triclinic, space group P 1 with a =9.529(12), b = 13.914(16), c = 14.906(17), V = 1903(4) 3, Z = 2, C45H34N6CoO7, Mr = 829.71,Dc = 1.448 g/cm3, F(000) = 858 and μ(MoKα) = 0.514 mm-1. The final R = 0.0655 and wR = 0.1136 for 6603 observed reflections with I 2σ(I) and R = 0.1136 and wR = 0.1747 for all data.     

A 3-fold Interpenetrated lvt Cd(Ⅱ) Network Constructed from 4-[(3-pyridyl)methylamino]benzoate Acid

A new three-dimensional(3D) coordination polymer, [Cd(L)2H2O]n·5nH2O 1 with 4-[(3-pyridyl)methylamino]benzoate acid(HL), has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a = 20.7937(16), c = 13.515(2), V = 5843.5(11) 3, C26H34CdN4O10, Mr = 674.97, Dc = 1.534 g/cm3, μ(MoKα) = 0.808 mm-1, F(000) = 2768, Z = 8, the final R = 0.0276 and wR = 0.0691 for 5323 observed reflections(I 2σ(I)). The result of thermal analysis shows that 1 is stable under 290 ℃. Moreover, it exhibits blue photoluminescence at room temperature.     

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 and Crystal Structure of a Novel Dinuclear Copper（Ⅱ） Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper(Ⅱ) complex [CuL(NO3)]2·2MeOH was obtained by the coordination reaction of Cu(NO3)2·3H2O with ligand HL (HL=N-(methyl-2-benzimidazol- methylidene)-2-hydroxyaniline). The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535(3), b=10.009(3), c=10.666(4) , α=104.303(4), β=100.105(4), γ=115.917(4)o, V=839.0(5) 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F(000)=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper(Ⅱ) complex units [CuL(NO3)]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper(Ⅱ) units.     

A New 2D Zinc(Ⅱ) Coordination Polymer Constructed by Imidazole-4,5-dicarboxylic Acid(H_3IDC) and 1,4-Bis(imidazol-1-ylmethyl)-benzene(bix)

A new 2D Zn(Ⅱ) coordination polymer [Zn(HIDC)(bix)0.5]n(1) was obtained by the hydrothermal reaction of ZnCl2,imidazole-4,5-dicarboxylic acid(H3IDC) and 1,4-bis(imidazol-1-ylmethyl)-benzene(bix) with a 2:2:1 mole ratio.X-ray diffraction crystal structural analysis reveals it crystallizes in monoclinic,space group P21/n with a = 12.125(3),b = 10.541(3),c = 12.484(3) ,β = 115.834(4)°,V = 1436.0(6) 3,Mr = 338.60,Z = 4,Dc = 1.566 Mg·m-3,F(000) = 684,μ(MoKα) = 1.730 mm-1,the final R = 0.0439 and wR = 0.0888 for 2101 observed reflections with I ≥ 2σ(I).In 1,each zinc(Ⅱ) ion is five-coordinated with a slightly distorted trigonal bipy-ramidal coordination geometry,and each μ2-HIDC2-acts as a bridge to bond two neighboring Zn(Ⅱ) ions,leading to a 1D zigzag chain architecture.The adjacent zigzag chains are further linked by μ2-bix to form an infinite 2D network structure.The fluorescence spectrum of 1 exhibits intense emission at 466 nm when excited at 397 nm in solid state at room temperature.     

A Zinc(Ⅱ) Coordination Framework Based on Terpyridine and 5-Nitroisophthalic Acid Mixed Ligands: Synthesis,Crystal Structure and Fluorescence Property

A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n(1, L1 = 4ˊ-(4-pyridyl)-4,2ˊ:6ˊ,4ˊˊ-terpyridine, 5-nipc = 5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.983(9), b = 13.709(3), c = 14.391(3)A, β = 114.93(4)°, V = 5364(2) A3, Dc = 1.493 g/cm3, C28H19N5O7 Zn, Mr = 602.85, F(000) = 2464, μ(Mo Kα) = 0.972 mm-1, Z = 8, R = 0.0935 and w R = 0.1509 for 4724 observed reflections(I 2σ(I)). The structure of 1 exhibits a three-dimensional(3D) network with a layer-pillar structure. The fluorescence property of 1 is also investigated.     

Controlled Self-assembly of Two Coordination Polymers via subtly Varying Bis（2-methyl imidazole） Ligands： from 3-Connected （6,3） Net to 4-Connected sql Net①

Two coordination polymers constructed from 3,4-thiophenedicarboxylic acid and bis(2-methyl imidazole) ligands, namely, {[Cd2(tdc)2(bip)2]·7H2O}n(1) and [Cd(tdc)(bib)]n(2)(H2tdc = 3,4-thiophenedicarboxylic acid, bip = 1,3-bis-(imidazol-2-methyl)propane and bib = 1,4-bis(imidazol-2-methyl)butane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analyses reveal that 1 exhibits a two-dimensional(2D) layered network with 3-connected(6,3) topology, which is further connected into a threedimensional(3D) supramolecular structure by intermolecular hydrogen bonds. However, 2 features a 2D network which can be rationalized as a 4-connected sql net. The results indicate the subtle difference of auxiliary bis(imidazol-2-methyl) ligands may lead to diverse architectures. Moreover, they exhibit luminescence emission in the solid state at room temperature.     

N,N'-二-[5-甲氧基-3-溴-2(5H)-4-呋喃酮基]-1,2-乙二胺的合成及其晶体结构(英文)

通过串联迈克尔加成-消除反应合成了N,N'-二-[5-甲氧基-3-溴-2(5H)-4-呋喃酮基]-1,2-乙二胺,利用IR、UV、1H NMR、13C NMR、MS、元素分析和X射线单晶衍射对其进行表征.X射线单晶衍射结果表明:标题化合物包含两个平面的呋喃酮环和两个手性中心,并通过N(1)-H(1A)…O(1)分子间氢键和Br(1)…O(2)近距离作用形成超分子结构.     

Synthesis and Characterization of a Manganese(Ⅱ) Coordination Compound with Two-dimensional Layer Structure: {[Mn_2(IP)_2(1,4-bdc)_2]·H_2O}n

A new complex {[Mn2(IP)2(1,4-bdc)2]·H2O}n(1)(IP = 1H-imidazo[4,5-f][1,10]-phenanthroline, 1,4-H2 bdc = 1,4-benzendicarboxylic acid), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a = 20.326(2), b = 24.249(2), c = 7.621(1), β = 108.546(6), V = 3561.2(7)3, Z = 4, Dc = 1.672 g/cm3, μ = 0.785 mm-1, F(000) = 1824, S = 1.067, the final R = 0.0299 and wR = 0.0752. Compound 1 possesses a 2D structural motif, in which two crystallographically independent 1,4-bdc dianions adopt the alternative mode of mixed bis(bidentate) and monodentate-bidentate coordination modes to bridge neighboring Mn(II) centers. And the 2D layers are linked up by hydrogen bonding and π···π stacking interactions to form a 3D network. The title compound has good thermal stability and exhibits photoluminescent emission maximum at 518 nm.