Structure of Coordination Polymer, 〔Zn(bipy)(H_2O)_3SO_4〕·2H_2O (bipy=4,4'-bipyridine)

1　INTRODUCTION4,4' bipyridine( bipy) is a good candidate for building open framework struc ture because of their rodlike rigidity and length.Framework structures formed bytransition metalsbridged by bipy vary with metaland anion.The structures of Zn bipy system include interpenetrating square grid sheets〔 Zn( bipy) 2 ( H2 O) 2 〕Si F6〔1〕,two dimensionallayer〔 Zn( bipy) ( H2 O) 4 〕( NO3) 2 · bipy〔2〕,〔 Zn( bipy) ( H2 O) 4 〕 ( NO3) 2 · 2 bipy· 3 H2 O〔2〕 and〔 Zn( bipy)…     

Synthesis, Crystal Structure and Characterization of the Coordination Polymer [Ni2(2-mpac)4(4,4'-bpy)·2H2O]n

Utilizing mononuclear complex Ni(2-mpac)2(H2O)2 as the molecular building block,a novel coordination polymer [Ni2(2-mpac)4(4,4'-bpy)·2H2O]n (1,2-mpac = 5-methyl-2-pyrazinecarboxylic acid, 4,4'-bpy = 4,4'-bipyridine) was successfully synthesized and structurally characterized by X-ray single-crystal diffraction method. Crystal data: monoclinic, space group C2/c, a = 23.870(1),b = 9.887(4), c = 18.929(9) (A),β= 126.840(5)°, V = 3575(3) (A)3, Z = 4, S = 1.046, μ = 1.594 mm-1,F(000) = 1768 and Dc = 1.127 g·cm-3. The final R = 0.0351 and wR = 0.0792 for 2372 observed reflections with Ⅰ＞ 2σ(Ⅰ) and R = 0.0564 and wR = 0.0938 for all reflections.     

Crystal Structure of a Threedimensional Coordination Polymer {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]·4H2O}n

A novel three-dimensional coordination polymer, {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]·4H2O}n, has been synthesized with oxydiacetate as bridge ligand and structurally determined by X-ray crystallography. The crystal belongs to monoclinic, space group C2/c with a = 17.805(2), b = 9.3923(12), c = 17.255(2)(A), β = 107.838(5)°, V = 2746.8(6) (A)3, Mr = 660.58, C12H28Ca3O23, Dc = 1.597 g/cm3, μ = 0.695 mm-1, Z = 4, F(000) = 1376, GOOF = 1.027, R = 0.0303 and wR = 0.0660. In the complex there are two coordination modes for Ca(Ⅱ) ions, one coordinated by three μ5-OOCCH2OCH2COO2- bridge ligands together with two H2O molecules, and the other by five μ5-OOCCH2OCH2COO2- bridge ligands. In both coordination modes each Ca(Ⅱ) ion assumes a distorted dipentapyramidal CaO7 geometry; whereas each oxydiacetate is coordinated with five Ca(Ⅱ) ions and acts as a pentdentates bridge ligand.     

Hydrothermal Synthesis and Structure of a Novel Coordination Polymer Co3(tma)(pda)2(H2O)3]n·nH2O

A novel coordination polymer [Co3(tma)(pda)2(H2O)3]n·nH2O was synthesized by hydrothermal reaction of 3-(3-pyridyl)acrylate acid (pda) and trimesic acid (tma) with CoCl2·6H2O. The structure was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal dif- fraction analysis. It crystallizes in triclinic, space group (P1)with a = 9.569(4), b = 12.562(6), c = 12.666(6)(A), α = 97.321(7), β = 110.295(7), γ = 106.110(7)°, V = 1328.9(10)(A)3, Dc = 1.877 g/cm3, Mr = 751.24, Z = 2, μ = 1.930 mm-1, F(000) = 758, the final R = 0.0392 and wR = 0.0837. The diffraction result shows that Co atoms are linked through pda and tma ligands to form an infinite three-dimensional network.     

Hydrothermal Synthesis, Crystal Structure and Fluorescence Property of a Novel Coordination Polymer [Eu2(C6H8O4)3(H2O)2]n·n(4,4''-bpy)

A novel coordination polymer [Eu2(C6H8O4)3(H2O)2]n·n(4,4’-bpy) (Mr = 928.51) was synthesized by the hydrothermal reaction of EuCl3·6H2O, adipic acid and 4,4’-bpy, and determined by elemental analysis, IR spectroscopy, thermal gravimetric analysis, single-crystal diffraction and fluorescence property. X-ray analysis reveals that a three-dimensional network has been formed between Eu3+ by carboxyl of adipic acid. The crystal is of orthorhombic, space group Pbcn with a = 21.870(7), b = 7.652(2), c = 19.624(6) (A), V = 3284.1(17)(A)3, Z = 4, Dc = 1.878 g/cm3, μ = 3.854 mm-1, F(000) = 1824, R = 0.0345 and wR = 0.0565. The coordination polymer exhibits intensive red light under UV excitation at room temperature, which is attributed to the 5D0→7F2 transition of Eu(Ⅲ) ions.     

Synthesis,Structure,Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[Cd[μ-(4,4'-dps) ]2(H2O)2]·(4-abs )2(H2O)2}n

A new cadmium(Ⅱ) compound,{[Cd[μ-(4,4'-dps) ]2(H2O)2]·(4-abs )2(H2O)2}n1(4,4'-dps=4,4'-dipyridylsulfide,4-abs=deprotonated 4-amino benzenesulfonic acid),has been synthesized and structurally characterized.It belongs to the orthorhombic system,space group Pbcn with a=19.950(3),b=10.6381(13),c=18.055(2) A,V=3831.8(8) A3,Z=4,C32H36CdN6O10S4,Mr=905.31,F(000)=1848,μ=0.850 mm-1,Dc=1.569 Mg/m3,the final R=0.0238 and wR=0.0589 for 3080 observed reflections with I > 2σ(I).Complex 1 is a one-dimensional linear chain coordination polymer and the repeat unit is comprised of doubly charged cadmium complex cation,uncoordinated 4-aminobenzene sulfonate anions and water molecules.The cadmium(Ⅱ) ion adopts a six-coordinate distorted octahedral geometry.Complex 1 is stabilized and linked into a three-dimensional layered structure through intermolecular O-H…O and N-H…O hydrogen bonds together with electrostatic force.The cyclic voltammograms and fluorescence spectrum of 1 were also measured.It shows one irreversible redox process and emits a very strong and sharp fluorescent band at about 341 nm.     

Two-Dimensional Coordination Polymer {[Zn(Pht)(4.4′-Bipy)(H2O)2] · 2H2O} n : Synthesis and Structure

The coordination polymer {[Zn(Pht)(4,4-Bipy)(H₂O)₂] · 2H₂O} _n (where Pht is a doubly deprotonated phthalic acid residue and 4,4-Bipy is 4,4-bipyridine) was synthesized and studied by X-ray diffraction. It was shown that both ligands perform a bridging function and unite the Zn atoms into a two-dimensional network with a periodicity of 11.302(2) Å (with 4,4-Bipy as the bridge) or 7.627(2) Å (with Pht as the bridge). The coordination polyhedron of Zn is a distorted octahedron with C ₂ symmetry. The Zn–N distances in the coordination polyhedron are 2.117(3) and 2.131(3) Å; the Zn–O_carb distance is 2.171(2) Å and the Zn–O(w) distance is 2.129(2) Å. The O–H···O hydrogen bonds involving the outer-sphere water molecules combine the polymer layers into a framework.     

Synthesis and Crystal Structure of a New Mixed-ligand Cluster[Mo3O4(C2O4)2bipy-(H2O3)]·EtOH·2H2O(bipy=2,2'-Bipyridine)

The novel mixed-ligand neutral compound [Mo3O4(C2O4)2·bipy(H2O)3]·EtOH·2H2O (bipy = 2,2'-bipyridine) has been prepared by the reaction of oxalic acid elution of Mo(Ⅳ) and bipy, and characterized by single-crystal X-ray diffraction analysis and IR. The crystal is of triclinic, space groups P1 with a = 9.5520(2), b = 10.3730(1), c = 13.5722(2) (A), α = 74.940(12), β = 80.772(14), γ = 69.898(11)°, V = 1215.73(11) (A)3, Z = 2, C16H24Mo3N2O18, Mr = 820.19, Dc = 2.241 g/cm3, μ = 1.616 mm-1, F(000) = 808, T= 293(2) K, the final R = 0.0424 and wR = 0.0939 for 4119 observed reflections with Ⅰ> 2σ(Ⅰ). The trinuclear unit is coordinated by mixed ligands of oxalate and bipy. The intermolecular hydrogen bonding interactions among adjacent [Mo3O4(C2O4)2·bipy(H2O)3] extend the compound into a therr-dimensional supramolecular framework. The uncoordinated water molecules and ethal molecules act as space-fillers and consolidate the whole architecture through hydrogen bonding interactions.     

Thermal decomposition reaction kinetics of complexes of [Sm(o-MOBA)3bipy]2·H2O and [Sm(m-MOBA)3bipy]2·H2O

The complexes of [Sm(o-MOBA)₃bipy]₂·H₂O and [Sm(m-MOBA)₃bipy]₂·H₂O (o(m)-MOBA = o(m)-methoxybenzoic acid, bipy-2,2′-bipyridine) have been synthesized and characterized by elemental analysis, IR, UV, XRD and molar conductance, respectively. The thermal decomposition processes of the two complexes were studied by means of TG–DTG and IR techniques. The thermal decomposition kinetics of them were investigated from analysis of the TG and DTG curves by jointly using advanced double equal-double steps method and Starink method. The kinetic parameters (activation energy E and pre-exponential factor A) and thermodynamic parameters (ΔH ^≠ , ΔG ^≠ and ΔS ^≠) of the second-step decomposition process for the two complexes were obtained, respectively.     

Hydrothermal Assembly and Structural Characterization of a Novel 3D Coordination Polymer: [Cd2Zn(BTC)2(H2O)4]n·2nH2O

A hydrothermal reaction of 1,3,5-benzene-tricarboxylic acid (H3BTC) with cad- mium acetate, zinc acetate and pyridine led to the formation of pink crystals of [Cd2Zn(BTC)2- (H2O)4]n·2nH2O 1. Single-crystal X-ray diffraction analysis has revealed that 1 (Cd2ZnC18H18O18) crystallizes in the monoclinic system, space group C2/c with a = 19.4328(7), b = 7.1420(3), c = 18.0426(5)(A), β = 118.035(1)o, V = 2210.3(1) (A)3, Mr = 812.49, Dc = 2.442 g/cm3, Z = 4, μ(MoKα) = 3.081 mm-1 and F(000) =1584. A total of 10735 reflections were collected, of which 2544 were unique. The structure was refined to R = 0.0200 and wR = 0.0603 for 2388 observed reflections with I>2σ(I). The crystal structure consists of cadmium(II)/zinc(II) carboxylates of BTC as well as coordination and discrete water molecules. Extension of the coordination geometry around three metal centers (Cd(1), Cd(2) and Zn(1)), two BTC3- ligands and four coordinated water molecules generates a three-dimensional coordination polymer.     

Structure of [NH3(CH2)4NH3]2P4O12·2H2O

After a short survey of what is the present state of the cyclophosphates associated with the organic molecule NH₂(CH₂)₄NH₂, we report chemical preparation and crystal structure for a new example of such compounds. [NH₃(CH₂)₄NH₃]₂P₄O₁₂.2H₂O is monoclinic (S.G. : P2₁/n), with Z = 2 and the following unit-cell parameters : a = 7.6728(8) Å, b = 18.962(3) Å, c = 7.9789(9) Å β = 111.751(9)°. Bidimensional layer arrangement of P₄O₁₂ rings connected to the water molecules thanks to weak H-bonds run parallel to the ab plane. The organic groupements located between these inorganic planes perform the three-dimensional cohesion by NH····O hydrogen bonds.     

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer: [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH = 2-benzoylbenzoic acid) was yielded by hydrothermal synthesis, determined by single-crystal X-ray diffraction, and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system, space group P with a = 9.112(3), b = 14.644(5), c = 27.076(11) (A), α = 84.223(3), β = 87.816(4), γ = 88.902(4)o, V = 3592(2) (A)3, C84H60O21Pr2, Mr = 1687.14, Z = 2, F(000) = 1700, Dc = 1.560 g/cm3, μ = 1.419 mm-1, the final R = 0.0485 and wR = 0.1258 for 13035 observed reflections with I＞2((I). The compound contains two different building units, [Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block, in which the Pr3 ion centers are both located in an eight-coordinated environment. However, in [Pr2(BYBA)6(H2O)2] the Pr3 ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

Synthesis, Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate: [Co(4,4'-bipy)2(H2O)4](4,4'-H2bipy)2[H2W12O40]·5.5H2O

A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'- H2bipy)2[H2W12O40]·5.5H2Ohas been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses, IR and UV spectroscopy, and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic, space group C2/c, with a = 21.315(9), b = 15.303 (7), c = 24.139(10) (A), β = 105.170(5)o, V = 7599(6) (A)3, Mr = 3706.99, Z = 4, F(000) = 6616, Dc = 3.231, μ = 18.395 mm-1, R = 0.0652 and wR = 0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2 cation, two diprotonated 4,4'-bipyridine molecules, 5.5 water molecules of crystallization, and one metatungstate polyoxoanion [H2W12O40]6-, which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O

The title complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O (C18H34Cl2CuN2O14S2) (tssb = taurine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3)nm, α = 103.800(4), β = 95.030(4), γ = 104.416(4)°, Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, μ = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are positioned diagonally on a plane.     

Synthesis and Structural Characterization of a Novel Coordination Polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O

At room temperature, a new three-dimensional organic-inorganic coordination polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O was synthesized by the reaction of Cd(CH3COO)2(2H2O, imidazole and fumaric acid. It was characterized by EA, IR, TG-DTA and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 8.980(3), b = 15.803(5), c = 13.415(4) (A), α = γ = 90.00°, β = 98.450(5)°, F(000) = 936, Mr = 466.73, Z = 4, V = 1883.0(10) (A)3, Dc = 1.646 g/cm3, μ(MoKα) = 1.201 mm-1, S = 1.041, the final R = 0.0237 and wR = 0.0469. The crystal structure shows that the cadmium has a distorted octahedral environment with three carboxyl oxygen donors and three imidazole nitrogen donors. Each cadmium atom is linked by a fumatate as bridging ligand to afford a one-dimensional framework, and then an infinite threedimensional supramolecular network is formed through hydrogen bonding interactions.     

Synthesis and Structure of an Interlock Network Frame of Cobalt( Ⅱ ) Coordination Polymer {[Co(azpy)2(NCS)2] · 1/4EtOH · 1/2H2O}n (azpy = 4,4' -Azobispyridine)

A compound {[Co(azpy)2(NCS)2]·1/4EtOH·1/2H2O}n(1), where azpy=4,4'- azo-bispyridine, was synthesized and characterized by means of IR, TGA-DTA, magnetic susceptibility and X-ray single crystal diffraction. It consists of two independent sets of fully interlocked two-dimensional networks with the dihedral angle 61. 7°, organized in parallel stacks of the sheets which are made of edge-shared [Co(Ⅱ)]4 squares separated by 0. 906 2 nm, and defined size rhombic channels. The thermal gravimetric analysis indicates that the framework is stable up to 198 C. The variable-temperature magnetic susceptibility measurements indicated that there is a weak antiferromagnetic interaction between the cobalt(Ⅱ) ions in the complex (1).     

Structure of the complex [trans-SnF4(H2O)2· (18-crown-6)· 2H2O]

The molecular and crystal structure of the title complex (I) obtained by addition of tin fluoride in a hydrofluoric acid solution to 18-crown-6 in methanol was investigated by X-ray structure analysis. The crystals are monoclinic, space group P2₁/n, a = 13.497(3), b = 7.806(2), c = 9.892(2) Å, β = 95.57(3)°, Z = 2 for C₁₂H₃₂F₄O₁₀Sn. In the polymer chain, the crown ether molecules alternate with the inorganic complexes [trans-SnF₄(H₂O)₂] and are linked to them by O-H...O type hydrogen bonds involving the intermediate water molecules. The weak C-H...F interactions bind the chains into the layers which are parallel to the xz plane.     

Synthesis and Crystal Structure of a New Dinuclear Copper(Ⅱ) Polymer: [Cu2(bipy)2(Hbtc)2(H2O)2]·(H2O)1/2

A new dinuclear copper(Ⅱ) polymer [Cu2(bipy)2(Hbtc)2(H2O)2]·(H2O)1/2 1 (bipy=2,2'-bipyridine, H3btc = benzene-1,3,5-tricarboxylic acid) was obtained by the hydrothermal single-crystal X-ray diffraction analysis and identified using elemental analysis and IR spectrum.The title complex crystallizes in monoclinic system, space group P21/c with a = 7.2880(5), b =18.4778(13), c = 13.5465(10)(A), β = 95.9580(10)°, C19H14.50CuN2O7.25, Mr = 450.37, V= 1814.4(2)(A)3, Z=4, Dc = 1.649 g/cm3, μ = 1.253 mm-1, F(000) = 918, Rint = 0.0185, the final R = 0.0271and wR = 0.0710 for 2773 observed reflections (I＞2σ(I)). The study results reveal that a pair of distorted square-pyramidal Cu2+ ions are interlinked by bis-monodentate bridging Hbtc2- ligands to constitute a 16-membered ring.     

Crystal Structure and Luminescence of a Europium Coordination Polymer {[Eu(p-MOBA)_3·2H_2O]·0.5H_2O· 0.5(4,4′-bipy)}_∞

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