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

A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 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 = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.     

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

A new metal-organic coordination polymer [Co(2-pya)2(4,4'-bipy)]2n·[(4,4'- bipy)0.5· H2O]2n(2-pya = 2-pyridinecarboxylic acid, 4,4'-bipy = 4,4'-bipyridine) 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 = 22.719(2), c = 10.710(2) A, V = 5527.8(14) A3, C54H46N10Co2O10, Mr = 1112.87, Dc = 1.337 g/cm3,μ(MoKα) = 0.665 mm-1, F(000) = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections (I ＞ 2σ(I)). It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4'-bipyridine.     

Synthesis and Crystal Structure of [Cd(NBA)(μ_3-OH)(4,4′-bipy)_(1/2)]_n

A new cadmium polymer [Cd(NBA)(μ3-OH)(4,4′-bipy)1/2]n 1 (NBA = m-nitrobenzoic acid and 4,4′-bipy = 4,4-bipyridine) has been synthesized by hydrothermal reaction. Its structure was determined by single-crystal X-ray diffraction method, and characterized by elemental analysis and IR spectrum. The crystal is of monoclinic, space group C2/c, with a = 15.6912(9), b = 25.9394(15), c = 6.7332(4) ′, β = 114.7700(10)°, V = 2488.4(3) 3, C12H9CdN2O5, Mr = 373.61, Z = 8, Dc = 1.995 g/cm3, μ = 1.776 mm-1, F(000) = 1464, R = 0.0411 and wR = 0.1128 for 2130 observed reflections (I > 2σ(I)). X-ray diffraction studies reveal that the compound features a layered structure, in which 4,4′-bipy ligands bridge Z type of double chains [Cd(μ3-OH)]n and NBA ligands locate at the two sides of the layer. The π-π interactions between the benzene rings of NBA ligands of two adjacent layers lead to the 3D framework.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(II)(C_6H_5CH=CHCOOH)_2(4,4′-bipy)(H_2O)_5]_n

A one-dimensional chain coordination polymer [Co(II)(C6H5CH=CHCOOH)2(4,4′- bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4′-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a = 1.1481(3), b = 1.1230(2), c = 1.1759(3) nm, β = 97.054(4)o, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z = 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(II) ions are linked together by one 4,4′-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(II) ion is coordinated with two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

一维链状镉(Ⅱ)配位聚合物{[Cd(PAc)2(4，4′-bipy)(H2O)]·4H2O}n的合成、晶体结构及热稳定性研究

A novel one-dimensional coordination polymer, {[Cd(PAc)₂(4,4-bipy)(H₂O)]·4H₂O}_n (HPAc=phenyl acetic acid, 4,4′-bipy=4,4′-bipyridine) was synthesized and characterized by element analysis, IR, TG and X-ray single diffraction crystal structure determination. It crystallizes in the monoclinic space group C2/c with a=2.088 5(4) nm, b=0.839 05(17) nm, c=1.683 5(3) nm, β=105.45(3)° and V=2.843 5(10) nm³, Z=4, M_r=628.94, F(000)=1 288, μ=0.820 mm^-1, R=0.019 9, wR=0.056 5. Each cadmium(Ⅱ) atom is seven-coordinated by four oxygen atoms from two different phenyl acetate groups and two nitrogen atoms from two 4,4′-pyridine ligands and one water molecule, forming a distorted pentagonal bipyramid coordination geometry. Adjacent cadmium(Ⅱ) atoms are bridged by 4,4′-pyridine ligand, constructing a infinite chain along the diagonal direction of ac plane. The Cd…Cd separation within the polymer is 1.164 6(4) nm. The three-dimensional supramolecular structures of the title complexes are constructed by hydrogen bonding interactions and π-π stacking interactions between the benzene rings of HPAc and 4,4′-bipy. CCDC: 616697.     

A Novel Three-dimensional Ni Coordination Polymer Based on Flexible Di-carboxylate Ligand and 4,4-Pyridine： Synthesis, Characterization and Topological Analysis

A novel Ni(II) coordination polymer [Ni(dtba)(4,4′-bpy)] (1, H2dtba = 2,2′-dithio- bisbenzoic acid, 4,4′-bpy = 4,4′-bipyridine) has been synthesized by H2dtba and Ni(CH3COO)2·4H2O with exo-bidentate rigid ligand 4,4′-bpy by using hydrothermal method, and its structure was determined by single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group Cc with a = 11.7624(9), b = 18.7933(19), c = 10.3071(11), β = 97.6510(10)°, V = 2258.2(4)3, Z = 4, C24H16N2NiO4S2, Mr = 519.22, Dc = 1.527 g/cm3, μ = 1.079 mm-1 and F(000) = 1064. The structure was solved by direct methods and refined to R = 0.0434 and wR = 0.1000 for 3281 observed reflections (I > 2σ(I)). The coordination environment of Ni(II) is a distorted octahedron, and a three-dimensional structure was formed with the coordination effect of dtba2- and 4,4′-bpy ligands. The topological analysis reveals that the whole framework of 1 is a 2-nodal net of (52.6)(53.64.72.8) topology. The thermal stability and XRD pattern of 1 were also investigated.     

Synthesis,Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn （NAA ）2（ 4,4′-bipy ） （H2O）4]n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

Synthesis and Crystal Structure of a 1D Alternate Chain Polymer [Zn2（NBA）2（4,4′-bipy）]n

A one-dimensional zinc-containing coordination polymer, [Zn2（NBA）2（4,4′-bipy）]n （NBA = 3-nitrobenzoic acid, 4,4′-bipy = 4,4′-bipyrindine）, has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, IR and elemental analysis. The crystal structure is of monoclinic, space group C2/c with a = 24.6478（2）, b = 14.0964（3）, c = 11.4275（2）A, β=108.7870（10）°, V = 3758.89（11） ,A^3, C38H20N6O16Zn2, Mr = 947.34, Z = 4, De = 1.674 g/cm^3 μ= 1.363 mml, F（000） = 1912, R = 0.0720 and wR = 0.2277 for 2841 observed reflections （I 〉 2σ（I）. In this compound, NBA in syn-syn coordination mode bridges zinc centers into dimericzinctetracarboxylate [Zn2（COO）4] secondary building units （SBUs） which are linked through μ-4,4′-bpy affording 1D alternating chains. These adjacent chains are further stacked through intermolecular π...π interactions to form a 3D framework.     

Solvothermal Synthesis and Structure Studies of a Mixed-valence Oxochloromolybdenum Complex

Emerald green crystals of a new mixed-valence oxochloromolybdenum complex,Mo(OH)2(2,2′-bipy)Cl2.[MoO(2,2′-bipy)Cl3]2, were obtained in an attempt to synthesize the Mo-S cluster compounds under solvothermal conditions. The title compound was characterized by EPR and X-ray single-crystal diffraction techniques. Crystallographic data: orthorhombic, space group Fdd2, a = 12.684(1), b = 21.518(2), c = 29.096(3)A, Mr = 1103.97, V= 7941(1)A^3, Z= 8, Dc =1.843 g/cm^3,μ= 1.514 mm^-1, F(000) = 4304, R = 0.0654 and wR = 0.1544 for 1944 observed reflections with 1 ≥/ 2σ(I). The compound consists of two different neutral molecules, Mo^IV-(OH)2(2,2′-bipy)Cl2 and MoVO(2,2′-bipy)Cl3. Both Mo^IV and Mo^V ions are in a distorted octahedral environment. The Mo(1)^IV atom is surrounded by two Cl^- ions and two O atoms from OH^- and two N atoms from a 2,2′-bipy ligand. The Mo(2) atom is surrounded by three Cl^- ions, one O^2- anion and two N atoms from another 2,2“-bipy ligand. The bipyridine occupies two cis-equatorial sites, while the Cl^- ions are located at the axial and equatorial positions.     

Two Zn~Ⅱ Coordination Polymers with 2,2?-Oxybis(benzoic acid) and Different N,N?-Donor ligands

Two new Zn~Ⅱ coordination polymers [Zn(oba)(4,4?-bipy)]n(1) and [Zn(oba)-(bpe)_(1/2)(H_2O)]_n(2)(H_2oba = 2,2?-oxybis(benzoic acid), 4,4?-bipy = 4,4?-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, IR spectroscopy and elemental analysis. Complex 1 shows a 3D metal-organic framework with a uninodal 4-connected 65.8 dmp network. Complex 2 features 1D ladder-shaped chains, which are further connected into a 2D stair-step network through intermolecular O–H···O hydrogen bonds.     

Synthesis,Crystal Structure and Luminescent Property of [Zn（C12H9O3）2（C10H8N2）]n·nH2O

Under hydrothermal condition, the reaction of 2-naphthoxyacetic acid with ZnCl2 and 4,4′-bipyridine （4,4′-bipy） has afforded a new Zn（Ⅱ） compound, [Zn（C12H9O3）2（C10H8N2）]n·nH2O1, which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of monoclinic, space group P21/c with a = 7.7335（2）, b = 19.3834（4）, c = 20.1707（4） A, β = 104.9830（10）°, V = 2920.82（11） A^3, C34H28ZnN2O7, Mr = 641.95, Z = 4, Dc = 1.460 g/cm^3,μ = 0.895 mm^-1, F（000） = 1328, R = 0.0406 and wR = 0.0876 for 4417 observed reflections （I〉 2σ（I）） Complex 1 consists of one-dimensional zigzag chains deriving from Zn（C12H9O3）2 units linked by 4,4′-bipy ligands, and lattice water molecules decorate between the chains. Non-covalent interactions, such as hydrogen-bonding and aromatic π-π interactions, lead to the formation of a 3D network structure. The thermogravimetric analysis （TGA） and luminescent property for 1 have also been studied in this paper.     

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(NAA)_2(4,4’-bipy)(H_2O)_4]_n

A novel one-dimensional chain coordination polymer [Mn(NAA)2(4,4’-bipy)(H2O)4]n has been synthesized with α-naphthaleneacetic acid, 4,4’-bipy and manganese(II) sulfate as raw ma-terials. Crystal data for this complex: monoclinic, space group P21/c, a = 1.1421(2), b = 1.6337(3), c = 0.94177(19) nm, β = 112.15(3)o, V = 1.6275(6) nm3, Dc = 1.407 g/cm3, Z = 2, μ(MoKα) = 0.467 mm-1, F(000) = 722, S = 1.007, R = 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese(II) ions are linked together by one 4,4?-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese(II) ion is coordinated with two oxygen atoms of two α-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4?-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

Synthesis, Crystal Structure and Fluorescene of a One-dimensional Compound {CdI_2(2,2′-bipy)}_n

The title compound, {CdI2(2,2′-bipy)}n, was prepared by the hydrothermal reac- tion of CdI2 and 2,2′-bipy in an aqueous solution, and its crystal structure was determined by X-ray single-crystal analysis. Crystallographic data for 1: C10H8N2CdI2, monoclinic system, space group C2/c, a = 16.927(1), b = 10.0925(7), c = 7.7422(3) , β = 106.0629(4)°, V = 1271.00(14) 3, Z = 4, F(000) = 944, μ = 6.546 mm-1, Dc = 2.730 g/cm3, Mr = 522.38, the final R = 0.0309 and wR = 0.0805 for 1310 observed reflections (I > 2σ(I)). X-ray crystal structure analysis shows that the Cd atom is coordinated by four iodines and two N atoms from one 2,2′-bipy to form an 1-D chain-like structure through bridging iodines. The fluorescene of the title compound was also discussed.     

Two Co(Ⅱ) Complexes Constructed from 1-(3,5-Dicarboxybenzyl)-3,5-pyrazole Dicarboxylic Acid:Syntheses,Structures and Magnetic Properties

Two new complexes[Co_2(L)(4,4′-bip)(H_2O)_3]_n (1) and{[Co(L′)_2(phen)]·2H_2O)}_n (2)(H_4L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_3L′=1-(3,5-dicarboxybenzyl)-3-pyrazole carboxylic acid,4,4′-bip=4,4′-bis(1-imidazolyl)biphenyl,phen=1,10-phenanthroline) were synthesized.Complexes 1 and 2have been characterized by IR spectrography,X-ray single-crystal diffraction,elemental analysis and thermogravimetry.1 crystallizes in monoclinic system,space group P2_1/c.Complex 2 crystallizes in monoclinic system,space group I2/a.It is remarkable that in situ hydrothermal decarboxylation was observed during preparing complex 2.In addition,magnetic analysis indicates that antiferromagnetic interaction exists among Co(Ⅱ) ions in complexes 1 and 2.     

A Novel Layered Complex with Rhomboidal Channels:Hydrothermal Synthesis, Crystal Structure, and Properties of Cu(4,4′-bipy)2(H2PO4)2(H2O)2 (bipy=bipyridine)

The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)2(H2PO4)2(H2O)2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)2(H2PO4)2(H2O)2 units. The copper atom, located on the crystallographic twofold axis, is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions, and two dihydrogen phosphate oxygen atoms at the axial positions, forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca. 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm, respectively. The two-dimensional networks are stacked parallelly on each other along c-axis to give an extended three-dimensional channel network with an interlayer distance of ca. 0.5030 nm. Crystal data: triclinic, space group P-1, a=1.0253(2) nm, b=1.4501(3) nm, c=0.79715(16) nm, α=97.91(3)°, β=90.99(3)°, γ=85.54(3)°, V=1.1703(4) nm3, Z=2, R=0.0892, wR=0.2451.     

{[Co(4，4′-bipy)(ambdc)(H2O)2](4，4′-bipy)(DMF)}n合成与晶体结构

A novel coordination polymer of {[Co(4,4′-bipy)(ambdc)(H₂O)₂](4,4′-bipy)(DMF)}_n has been synthesized using 5-aminoisophthalic acid (H₂ambdc), 4,4′-bipyridine(4,4′-bipy) and metal salts. The ambdc ligand in title compound has a μ₂-monodentate coordination mode and the structure of the title compound is a two-dimensional network. CCDC: 279054.     

DNA-binding Studies of Two Silver(I)-sulfonate Complexes Constructed by In Situ Reaction

Two silver(I)-sulfonate complexes,[Ag(NO_3)(4,4'-bipy)][Ag(HL)(4,4'-bipy)]·2H_2O(1) and[Ag(H_2O)(4,4'-bipy)][AgL(4,4'-bipy)]·2H_2O(2),have been synthesized by in situ reaction(H_2L = 2-formylbenzenesulfonic acid,4,4-bipy = 4,4-bipyridine).1 displays two parallel 1D chains expending to a 3D supramolecule by n—n interactions and O-H…O hydrogen bonds,in which the[Ag(NO_3)]or[Ag(HL)]units are joined by bridging 4,4'-bipy molecules,respectively.The interactions between the complexes and DNA were studied by means of fluorescence spectra and surface-enhanced Raman scattering(SERS) spectra.The special configuration and intercalation effects between 1 and DNA are stronger than that between 2 and DNA.     

Synthesis,Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn(II) coordination polymer [Zn3(BTC)2(4,4'-bpy)(CO)2]n(1, H3 BTC =1,3,5-benzenetricarboxylic acid, 4,4'-bpy = 4,4'-bipyridine) has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262(3), b = 18.838(5), c =15.083(4) A, β = 99.203(4)o, V = 2878.3(14) A3, C30H14Zn3N2O14, Mr = 822.54, Z = 4, Dc = 1.898g/cm3, μ = 2.561 mm-1, F(000) = 1640, R = 0.0363 and w R = 0.0932 for 2828 observed reflections(I 2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(II) atoms which are connected by BTC3- ligands and 4,4'-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Syntheses and Crystal Structures of Two New Metal Phosphonates： [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] and [Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2）

By the reactions of manganese（if） acetate, 2-sulfoethylphosphonic acid, 1,10-phen （1,10-phen = 1, 10-phenanthroline） or cobalt（Ⅱ） acetate, 4,4＇-bipy and 2-carboxyethylphosphonic acid, two novel compounds of [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] （1） and[Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2） （2） have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Compound 1 has a 0D structure. Two Mn（ii） ions are linked by two 2-carboxyethylphosphonic acid ligands, forming a centrosymmetric dimer. These dimers are further interlinked into a 2D layer structure by π-π stacking interactions and hydrogen bonds. Compound 2 has a 1D chain structure. The 2-carboxyethylphosphonic acid remains uncoordinated and acts as the organic template. By the bridge of 4,4＇-bipy, the [Co（4,4＇-bipy）]^2＋ chains are formed.