Hydrothermal syntheses and crystal structures of complex-linked three-Dimensional coordination vanadium selenites: M(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (M = Co,Ni)

Two inorganic-organic hybrid compounds with the formula M(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (M = Co, Ni) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds Co(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (1) and Ni(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (2), which are structural analogues, crystallize in the triclinic space group Ponemacr; with crystal data a = 7.9665(3) A, b = 8.1974(3) A, c = 13.8096(4) A, alpha = 85.704(2) degrees, beta = 73.5180(10) degrees, gamma = 75.645(2) degrees, V = 837.76(5) A(3), and Z = 2 and a = 7.9489(19) A, b = 8.128(2) A, c = 13.709 A, alpha = 85.838(6) degrees, beta = 73.736(8) degrees, gamma = 75.594(9) degrees, V = 823.5(4) A(3), and Z = 2, respectively. [M(4,4'-bipy)(H(2)O)V(2)Se(2)O(10)] (M = Co, Ni) have a three-dimensional structure and consist of two subunits, [(VO(2))(SeO(3))](-) infinite chains and [M(4,4'-bipy)(H(2)O)](2+) fragments. The [(VO(2))(SeO(3))](-) chains are composed of [V(2)Se(4)O(14)](4)(-) clusters linked by VO(4)N triangular bipyramids. The 4,4'-bipy molecule as a bifunctional organic ligand is directly linked to Co or Ni and V atoms, affording the three-dimensionality. The compounds were characterized by infrared spectroscopy and differential thermal and thermogravimetric analyses.     

Syntheses, structures, and optical properties of novel zinc(ii) complexes with multicarboxylate and N-donor ligands

Five novel coordination polymers [Zn(2)(OA)(4,4'-bipy)(H(2)O)].0.5(4,4'-bipy), [Zn(2)(OA)(dib)(H(2)O)].H(2)O, [Zn(2)(OA)(bbi)(2)].3H(2)O, [Zn(2)(OA)(phen)(2)(H(2)O)] and [Zn(4)(OA)(2)(2,2'-bipy)(2)(H(2)O)].2H(2)O were obtained by hydrothermal reactions of Zn(NO(3))(2).6H(2)O with a V-shaped multicarboxylate ligand 3,3',4,4'-oxydiphthalic acid (H(4)OA) and a series of N-donor ligands, namely 4,4'-bipyridine (4,4'-bipy), 1,4-di(1-imidazolyl)benzene (dib), 1,1'-(1,4-butanediyl)bis(imidazole) (bbi), 1,10-phenanthroline (phen), 2,2'-bipyridine (2,2'-bipy). The structures of the complexes were established by single-crystal X-ray diffraction analysis. Complex exhibits a robust 3D porous structure with uncoordinated 4,4'-bipy molecules filling the cavities. Complexes and show a complicated 3D framework, while complexes and have a 2D network and a 1D helical chain structure, respectively. The results indicate that the multicarboxylate OA(4-) ligand can adopt varied coordination modes in the formation of the complexes and the influence of the N-donor ligand on the structure of the complexes is discussed. The photoluminescence properties of H(4)OA and were studied in the solid state at room temperature. Moreover, nonlinear optical measurements showed that displayed a second-harmonic-generation (SHG) response of 0.5 times of that for urea. The results suggested that the configuration and flexibility of the ligands play a key role in directing the related properties of the complexes.     

Synthesis, Crystal Structure and Water-induced Reversible Crystal-to-amorphous Transformation Property of [{Ni(IBG)(4,4'-bipy)(a2O)2}·3a2O]n

A novel NiⅡ complex[{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n1(H2IBG=isophthaloylbisglycine and 4,4'-bipy=4,4'-bipyridine)has been synthesized and characterized by singlecrystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis.It crystallizes in monoclinic,space group P2/c with a=15.5420(7),b=22.4344(1),c=8.3455(5)(A),β=101.538(3)°,V=2670.1(7)(A)3,Z=4,C22H32N4NiO13,Mr=619.23,Dc=1.443 g/cm3,F(000)=1296.0,μ(MoKa)=0.750 mm-1,the final R=0.0570 and wR=0.1445 for 2296 observed reflections with I>2σ(I).In the structure,the NiⅡ metal center is coordinated in an octahedral environment arranged by two water molecules,two carboxylate oxygen atoms and two nitrogen atoms from two4,4'-bipy ligands.Thermal decomposition and powder X-ray diffraction results indicate that the transformation from the crystal form,[{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n,to the amorphous powder,Ni(IBG)(4,4'-bipy)(H2O)2,is reversible,so the latter form may be utilized as an absorbing agent for water and water vapor.     

Novel hydrogen-bonded three-dimensional networks encapsulating one-dimensional covalent chains: [M(4,4'-bipy)(H2O)(4)](4-abs)(2).nH2O (4,4'-bipy = 4,4'-bipyridine; 4-abs = 4-aminobenzenesulfonate) (M = Co,n = 1; M = Mn,n = 2)

Two novel compounds, [Co(4,4'-bipy)(H(2)O)(4)](4-abs)(2).H(2)O (1) and [Mn(4,4'-bipy)(H(2)O)(4)](4-abs)(2).2H(2)O (2) (4,4'-bipy = 4,4'-bipyridine; 4-abs = 4-aminobenzenesulfonate), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses, UV-vis and IR spectra, and TG analysis. X-ray structural analysis revealed that 1 and 2 both possess unusual hydrogen-bonded three-dimensional (3-D) networks encapsulating one-dimensional (1-D) covalently bonded infinite [M(4,4'-bipy)(H(2)O)(4)](2+) (M = Co, Mn) chains. The 4-abs anions in 1 form 1-D zigzag chains through hydrogen bonds. These chains are further extended through crystallization water molecules into 3-D hydrogen-bonded networks with 1-D channels, in which the [Co(4,4'-bipy)(H(2)O)(4)](2+) linear covalently bonded chains are located. Crystal data for 1: C(22)H(30)CoN(4)O(11)S(2), monoclinic P2(1), a = 11.380(2) A, b = 8.0274(16) A, c = 15.670(3) A, alpha = gamma = 90 degrees, beta = 92.82(3) degrees, Z = 2. Compound 2 contains interesting two-dimensional (2-D) honeycomb-like networks formed by 4-abs anions and lattice water molecules via hydrogen bonding, which are extended through other crystallization water molecules into three dimensions with 1-D hexagonal channels. The [Mn(4,4'-bipy)(H(2)O)(4)](2+) linear covalent chains exist in these channels. Crystal data for 2: C(22)H(32)MnN(4)O(12)S(2), monoclinic P2(1)/c, a = 15.0833(14) A, b = 8.2887(4) A, c = 23.2228(15) A, alpha = gamma = 90 degrees, beta = 95.186(3) degrees, Z = 4.     

Hydrothermal syntheses, crystal structures, and magnetic properties of inorganic-organic hybrid vanadium selenites with zero- to three-dimensional structures: (1,10-phenanthroline)(2)V(2)SeO(7), (2,2'-bipyridine)VSeO(4), (4,4'-bipyridine)V(2)Se(2)O(8), and (4,4'-bipyridine)(2)V(4)Se(3)O(15).H(2)O

A family of inorganic-organic hybrid vanadium selenites with zero-, one-, two-, and three-dimensional structures, (1,10-phen)(2)V(2)SeO(7), (2,2'-bipy)VSeO(4), (4,4'-bipy)V(2)Se(2)O(8), and (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O (where phen = phenanthroline and bipy = bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Different bidentate organodiamine ligands and reactant concentrations were used in the four reaction systems, which are responsible for the variety of structural dimensions of the compounds. (1,10-phen)(2)V(2)SeO(7) crystallizes in a monoclinic system with space group P2(1)/n and cell parameters a = 8.6509(3) A,( )b = 7.8379(2) A, c = 34.0998(13) A, beta = 91.503(2) degrees, and Z = 4. (2,2'-bipy)VSeO(4) crystallizes in a monoclinic system with space group C2/c and cell parameters a = 17.0895(12) A, b = 14.7707(10) A, c = 11.7657(8) A, beta = 131.354(3) degrees, and Z = 8. (4,4'-bipy)V(2)Se(2)O(8) crystallizes in a triclinic system with space group Ponemacr; and cell parameters a = 7.1810(10) A, b = 10.8937(13) A, c = 11.1811(15) A, alpha = 115.455(3) degrees, beta = 107.582(3) degrees, gamma = 91.957(4) degrees, and Z = 2. (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O crystallizes in a monoclinic system with space group Pc and cell parameters a = 7.9889(9) A, b = 7.8448 A, c = 23.048(3) A, beta = 99.389(4) degrees, and Z = 2. (1,10-phen)(2)V(2)SeO(7) has an isolated structure, (2,2'-bipy)VSeO(4) has a chain structure, (4,4'-bipy)V(2)Se(2)O(8) has a layered structure, and (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O has a framework structure. The chains are constructed from VO(4)N(2) octahedra and SeO(3) pyramids, laced by organic ligands (2,2'-bipy). The layers consist of vanadium selenite chains [(VO)(2)(SeO(3))(2)]( infinity ), linked by 4,4'-bipy molecules. The framework is composed of vanadium selenite sheets [V(4)Se(3)O(16)]( infinity ), pillared by 4,4'-bipy molecules. All of the compounds are thermally stable to 300 degrees C, and the magnetic susceptibilities confirm the existence of tetravalent V atoms in the antiferromagnetic (4,4'-bipy)V(2)Se(2)O(8) complex and mixed tetravalent and pentavalent V atoms in the paramagnetic complex (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O.     

Syntheses, structures, and properties of five coordination polymers containing fluorescent whitener

Fluorescent whitener (4,4'-bis(2-sulfonatostiryl)biphenyl) was incorporated with M/4,4'-bipy (M=Cd, Co; 4,4'-bipy=4,4'-bipyridine) 2D frameworks, Mn/4,4'-bipyH fragment, and the [Zn2(Im)2(ImH)4]2+ (ImH=imidazole) chain under hydrothermal conditions to obtain seven new coordination polymers: [Cd(4,4'-bipy)(L)(H2O)2] (1), [Co(4,4'-bipy)2(L)].2H2O (2), [Co(4,4'-bipy)2(H2O)2](4,4'-bipy)(L).2H2O (3), [Mn(4,4'-bipyH)2(L)2(H2O)2].4H2O (4), and [Zn2(Im)2(ImH)4](L) (5). Their structures were determined by single-crystal X-ray diffraction. In 1, binuclear [Cd2] units are bridged by 4,4'-bipys into a 2D cationic framework, which is further penetrated by L anions. 2 has an organic-inorganic hybrid layer consisting of [Co(4,4'-bipy)2] squarelike motifs and L anions. 3 features a pcu-like 3D cationic framework with the inclusion of L anions. In 4, the [Mn(4,4'-bipyH)2(H2O)2]4+ cationic fragment is sandwiched by L anions into a sandwichlike hybrid layer. 5 exhibits a 3D honeycomb-like structure with each nanotube encapsulating two parallel L anionic chains. TGA and PXRD indicate solids 1, 4, and 5 are thermally stable up to 280, 200, and 250 degrees C under an air atmosphere, respectively. 1 has bright blue-green luminescence with a peak maximum band at about 470 nm. 4 exhibits tunable emission between dark-red and weak-green under the excitation of 500 and 280 nm, respectively. 5 displays a bright blue-green emission with a peak band at 454 nm and a shoulder peak at 473 nm. It is attractive that the luminescent properties of solids 1, 4, and 5 are almost retained after heat treatment at 200, 200, and 250 degrees C for 2 h under an air atmosphere, respectively.     

两个双核Cu(Ⅰ)-4，4′-联吡啶配合物的合成、结构和光谱分析

采用乙醚蒸汽扩散法,由四氟合硼酸四乙腈合铜(Ⅰ)、4,4′-联吡啶、二(2-二苯基膦基)苯基醚或者三苯基膦的反应后的二氯甲烷和乙腈混合溶液中,晶化出[Cu₂(4,4′-bipy)(POP)₂(CH₃CN)₂(C₂H₅O)₂](BF₄)₂ (1)和[Cu₂(4,4′-bipy)(PPh₃)₄(CH₃CN)₂](BF₄)₂ (2)两种配合物。对它们进行了元素分析和X射线衍射单晶结构表征,同时测定了UV-Vis光谱及相应的激发态寿命。配合物1和2展示了较好的光物理特性,在275 nm紫外光的激发下,固体粉末样品的最大发射峰位分别位于527和483 nm,这归因于金属干扰的配体内部跃迁。     

一维链状锰配合物的合成、结构及磁性研究

合成了邻硝基苯磺酰化丙氨酸配体2-NBS-AlaH (1)(2-NBS-AlaH=邻硝基苯磺酰化丙氨酸)及其锰的配合物[Mn(4，4′-bipy)(H₂O)₄]₂[(4，4′-bipy)₂(H₂O)₃(2-NBS-Ala)₄] (2)。通过X-射线单晶衍射测定了其结构：配体通过氢键形成了一维链状结构；配合物2中，4，4′-bipy把锰离子连成了一维链状结构。磁性研究表明，配合物由于分子间的自旋耦合呈现出弱的铁磁性。     

Synthesis,Crystal Structure and Water-induced Reversible Crystal-to-amorphous Transformation Property of [{Ni(IBG)(4,4'-bipy)(H_2O)_2}·3H_2O]_n

A novel NiII complex [{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n 1 (H2IBG = isophthaloylbisglycine and 4,4'-bipy = 4,4'-bipyridine) has been synthesized and characterized by singlecrystal X-ray diffraction, elemental analysis, IR spectra and thermogravimetric analysis. It crystallizes in monoclinic, space group P2/c with a = 15.5420(7), b = 22.4344(1), c = 8.3455(5), β = 101.538(3)o, V = 2670.1(7)3, Z = 4, C22H32N4NiO13, Mr = 619.23, Dc = 1.443 g/cm3, F(000) = 1296.0, μ(MoKα) = 0.750 mm-1, the final R = 0.0570 and wR = 0.1445 for 2296 observed reflections with I 2σ(I). In the structure, the NiII metal center is coordinated in an octahedral environment arranged by two water molecules, two carboxylate oxygen atoms and two nitrogen atoms from two 4,4'-bipy ligands. Thermal decomposition and powder X-ray diffraction results indicate that the transformation from the crystal form, [{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n, to the amorphous powder, Ni(IBG)(4,4'-bipy)(H2O)2, is reversible, so the latter form may be utilized as an absorbing agent for water and water vapor.     

Synthesis and Crystal Structure of [Cd(NBA)(μ3-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)(A), β=114.7700(10)°, V=2488.4(3)(A)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.     

A series of new organic-inorganic molybdenum arsenate complexes based on [(ZnO6)(As3O3)2Mo6O18]4- and [HxAs2Mo6O26](6-x)- clusters as SBUs

By synthesizing the novel molybdenum arsenate complexes, we have obtained eight new structures, namely, (4,4'-bipy)[Zn(4,4'-bipy)2(H2O)2]2[(ZnO6)(AsIII3O3)2Mo6O18].7H2O, 1, [Zn(phen)2(H2O)]2[(ZnO6)(AsIII3O3)2Mo6O18].4H2O, 2, [Zn(2,2'-bipy)2(H2O)]2[(ZnO6)(AsIII3O3)2Mo6O18].4H2O, 3, [Zn(H4,4'-bipy)2(H2O)4][(ZnO6)(AsIII3O3)2Mo6O18].8H2O, 4, (H24,4'-bipy)[CuI(4,4'-bipy)]2[H2AsV2Mo6O26].H2O, 5, (H24,4'-bipy)3[AsV2Mo6O26].4H2O, 6, (H24,4'-bipy)3[AsV2Mo6O26(H2O)].4H2O, 7, and (H24,4'-bipy)2.5(H3O)[AsV2Mo6O26(H2O)].1.25H2O, 8 (4,4'-bipy = 4,4'-bipyridine, 2,2'-bipy = 2,2'-bipyridine, phen = 1,10-phenanthroline). These structures were determined by single-crystal X-ray diffraction analysis and were further characterized by elemental analysis, IR, XPS spectroscopy, and TG analysis. The structure of 1 is constructed from two-dimensional square gridlike sheets linked by the polyanions [(ZnO6)(AsIII3O3)2Mo6O18]4- via hydrogen-bonding interactions to form a three-dimensional supramolecular framework with two types of channels. Compounds 2 and 3 display similar bisupported structures. Compound 4 features a three-dimensional supramolecular architecture. Compound 5 possesses a 1D infinite ladderlike ribbon. Compounds 6-8 are discrete structures exhibiting three isomeric forms of [HxAs2Mo6O26](6-x)-. Furthermore, compound 8 represents a new isomer B'-[As2Mo6O26(H2O)]6-. In addition, the fluorescent properties of compounds 1-3 are reported.     

Magneto-structural xorrelations in 2D and 3D extended structures of manganese(II)-malonate systems

Two polymeric malonato-bridged manganese(II) complexes of formula [Mn(mal)(H(2)O)(2)](n)() (1) and [Mn(2)(mal)(2)(4,4'-bipy)(H(2)O)(2)](n)() (2) have been synthesized and characterized (mal = malonate dianion; 4,4'-bipy = 4,4'-bipyridine). The crystal structure of complex 1 was already known. Complex 2 crystallizes in monoclinic space group P2(1)/n, Z = 2, with unit cell parameters of a = 7.2974(10) A, b = 18.7715(10) A, c = 7.514(3) A, and beta = 91.743(12) degrees. The structure determination reveals that the complex [Mn(2)(mal)(2)(4,4'-bipy)(H(2)O)(2)](n)() (2) is a 3D network being composed of Mn-malonate sheets which are pillared by bidentate 4,4'-bipy spacer forming small voids. The Mn-Mn distances through Mn-mu-(O3-C8-O4)-Mn, Mn-mu(O1-C6-O2)-Mn, and Mn-mu-4,4'-bipy-Mn bridges are 5.561, 5.410, and 11.723 A, respectively. The magnetic behaviors of complexes 1 and 2 in the temperature range 300-2 K are very close, corresponding to a weak antiferromagnetic coupling. The magnetic pathways of complex 1 are through two Mn-O-C-O-Mn with anti-anti conformation and two Mn-O-C-O-Mn with syn-anti conformations and in complex 2 through all Mn-O-C-O-Mn with syn-anti conformations. Both syn-anti and anti-anti conformations create weak antiferromagnetic coupling, and the susceptibility data are fitted by the expansion series of Lines and the Curély formula for an S = 5/2 antiferromagnetic quadratic layer, based on the exchange Hamiltonian H = -Sigma(nn)()JS(i)()S(j)(). The best fit is given by the superexchange parameters J = -0.32 cm(-)(1) and g = 2.00 for complex 1 and J = -0.14 cm(-)(1), J(inter) = -0.031 cm(-)(1), and g = 2.00 for complex 2. Finally, in both the complexes there is a magnetic pathway Mn-O-C-C-C-O-Mn, and this pathway through the three carbon atoms of the malonato-bridging ligand could be considered negligible.     

Hydrothermal Synthesis,Crystal Structure and Characterization of a New Keggin Polyoxometalate {[Ag~I(4,4’-bipy)]_3[PW_(12)O_(40)]}·(4,4’-bipy)

A novel polyoxometalate {[AgI(4,4'-bipy)]3[PW12O40]}·(4,4'-bipy)·4H2O 1 has been synthesized hydrothermally and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal of 1 belongs to the triclinic system, space group P1 with a = 11.3710(17), b = 12.0701(16), c = 13.1061(12) , α = 112.838(3), β = 94.545(6), γ = 99.526(4)°, V = 1614.4(4) 3, Mr = 3825.40, Z = 1, Dc = 3.935, μ = 22.289mm-1, F(000) = 1692, the final R = 0.0507 and wR = 0.1054. X-ray diffraction analysis reveals that the molecular structure of 1 consists of three coordinated cations [AgI(4,4'-bipy)]+, a polyanion unit [PW12O40]3-, and a discrete 4,4′-bipy molecule. Significantly, there exist two crystallographically independent silver(I) centers in 1 and all [AgI(4,4'-bipy)]+ cations are linked with each other to form a one-dimensional Ag-4,4'-bipy polymer chain. The neighboring polymer chains are further interconnected to form a 3D framework by the covalent effect of silver atoms and terminal oxygen atoms of the polyanion. The electrochemical behaviors of 1 have also been studied in detail by cyclic voltammograms.     

二维配位聚合物[Cu(μ-Ⅰ)(μ-4,4-bipy)]n的溶液合成与晶体结构

碘化亚铜和4,4'-二联吡啶在溶液中反应的二种方法可制备出标题化合物的2个不同红色晶体,结构表征出两种晶体分别是单斜C2/c(1)和四方I41/acd(2)空间群.在[Cu(μ-Ⅰ)(μ-4,4-bipy)]n结构中,铜原子是处于与2个碘原子和2个相互扭曲4,4'-二联吡啶中的氮原子的扭曲四面体配位环境中,2个[Cu(μ-Ⅰ)]2单元和2个桥式4,4'-二联吡啶配体形成1个[Cu2(μ-Ⅰ)2(μ-4,4-bipy)]2直角单元,4个直角单元经4个4,4'-二联吡啶侧式桥联而形成1个大的八角环,并由此与直角单元相互垂直而形成1个二维框架结构.     

Assembled bright green fluorescent zinc coordination polymer

A 1D zinc coordination polymer with bright green fluorescence, [Zn(4,4'-bipy)(H2O)4][Zn(4,4'-bipy)(1.5)(L)(H2O)2]2(L).6H2O (L = 4,4'-bis(2-sulfonatostyryl)biphenyl), has been designed, hydrothermally synthesized and characterized; the interesting structure consists of three types of infinite chain: a neutral sandwich-like chain, ionic and cationic chains.     

Syntheses, structures, and characterizations of four new lead(II) 5-sulfosalicylate complexes with both chelating and bridging neutral ligands

Four structurally diverse complexes, {[Pb(Hssal)(2,2'-bipy)](4,4'-bipy)0.5}n (1), [Pb2(Hssal)2(2,2'-bipy)2(4,4'-bipy)(H2O)2] (2), [Pb(Hssal)(phen)(4,4'-bipy)0.5]n (3), and [Pb(Hssal)(2,2'-bipy)(bpe)0.5]n (4), have been synthesized and characterized by elemental analyses, IR, thermogravimetric analyses, fluorescent spectra, and single-crystal X-ray analyses, where Hssal2- is doubly deprotonated 5-sulfosalicylate, 2,2'-bipy is 2,2'-bipyridine, phen is 1,10-phenanthroline, 4,4'-bipy is 4,4'-bipyridine, and bpe is trans-1,2-bis(4-pyridyl)ethylene. The structure of complex 1 possesses a one-dimensional ladderlike chain with guest 4,4'-bipy molecules, while the molecular structure of complex 2 is a dimeric species with a coordinating 4,4'-bipy ligand. Complex 3 consists of a one-dimensional ladderlike chain with monodentate 4,4'-bipyridine but somewhat different from that of complex 1. Complex 4 is a two-dimensional layer structure. In 1-4, all 5-sulfosalicylates are doubly deprotonated, and all carboxylate groups of Hssal2- chelate to PbII ions; however, the coordination modes of sulfonyl groups are different: syn-syn bridging in 1, noncoordinating in 2, syn-skew bridging in 3, and one-atom bridging in 4. The noncoordinating mode of sulfonate in PbII complexes containing 5-sulfosalicylate is first reported in this presentation. The 4,4'-bipy ligands act as guest molecules in 1, dimeric linkers in 2, and monodentates in 3. The pi-pi stacking interactions can be observed in complexes 1-3, whereas there is no such interaction in complex 4. The coordination spheres of PbII ions in 1-4 are controlled by three factors: the activity of a lone pair of electrons, weak Pb-O interactions, and pi-pi stacking interactions. The PbII lone pair in 4 is inactive, whereas in 1-3, they are stereochemically active. The thermal stability and fluorescent property of complexes 1-4 are different from those of PbII complexes only containing chelating ligands, [Pb(Hssal)(2,2'-bipy)(DMF)]n (5), and [Pb(Hssal)(2,2'-bipy)(H2O)]n (6), and [Pb(Hssal)(phen)(DMF)]n (7).     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4''-bipy)(H2O)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)°, 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.     

Synthesis, characterization, and crystal structures of three new divalent metal carboxylate-sulfonates with a layered and one-dimensional structure

Hydrothermal reactions of 5-sulfoisophthalic acid (HO(3)SC(6)H(3)-1,3-(CO(2)H)(2), H(3)L) with M(II) carbonate (or oxide) and 4,4'-bipyridine (4,4'-bipy) (or 2,2'-bipyridine, 2,2'-bipy) resulted in three new metal carboxylate-sulfonate hybrids, namely, [CdL(H-4,4'-bipy)] (1) and [Cd(3)L(2)(2,2-bipy)(4)(H(2)O)(2)].2H(2)O (2) with layered structures and [ZnL(H-4,4'-bipy)(H(2)O)].2H(2)O (3), whose structure features a one-dimensional double chain. The cadmium(II) ion in complex 1 is seven-coordinated by five carboxylate oxygen atoms and one sulfonate oxygen atom from four ligands and a unidentate 4,4'-bipyridine. The interconnection of the cadmium(II) ions through bridging carboxylate-sulfonate ligands resulted in the formation of a <002> double layer with the bipyridyl rings orientated toward the interlayer space. Complex 2 has a different layered structure. Cd(1) is seven-coordinated by two bidentate chelating carboxylate groups from two ligands, a bidentate chelating 2,2'-bipy and an aqua ligand, and Cd(2) is octahedrally coordinated by two bidentate chelating 2,2'-bipy's, a sulfonate oxygen, and an aqua ligand. The coordination geometry around Cd(3) is similar to that of Cd(1) with the aqua ligand being replaced by an oxygen atom from the sulfonate group. The carboxylate-sulfonate ligand acts as pentadentate ligand, bridging with three cadmium(II) ions. The bridging of cadmium(II) ions through the carboxylate-sulfonate ligands resulted in the formation of <006> and <003> layers; the 2,2'-bipy molecules and [Cd(2)(2,2'-bipy)(2)(H(2)O)] cations are orientated to the interlayer space. Complex 3 features a 1D metal carboxylate-sulfonate double chain along the diagonal of the a- and b-axes. The zinc(II) ion is octahedrally coordinated by four carboxylate O atoms from three ligands, a unidentate 4,4'-bipy, and an aqua ligand. Each pair of zinc(II) ions is bridged by two carboxylate groups from two ligands to form a dimer, and such dimeric units are interconnected by bridging ligands to form a double chain. The sulfonate group of the carboxylate sulfonate ligand remains noncoordinated and forms a number of hydrogen bonds with aqua ligands as well as lattice water molecules.     

Hydrothermal synthesis, crystal structure, conductivity, and thermal decomposition of [Cu(4,4'-bipy)(H2O)(Mo3O10)].H2O

The hydrothermal reaction of (NH(4))(6)Mo(7)O(24).4H(2)O, CuCl(2).2H(2)O, and 4,4'-bipyridine yields bipyridine-ligated copper-trimolybdate monohydrate [Cu(4,4'-bipy)(H(2)O)(Mo(3)O(10))].H(2)O in the monoclinic system with space group of C(2/c) and cell parameters of a = 15.335(2) A, b = 15.535(2) A, c = 15.106(2) A, beta = 101.162(2) degrees, V = 3530.7(9) A(3), and Z = 8. Its structure consists of one-dimensional infinite ([Mo3O10]2-)( infinity ) chains linked through [Cu2(H2O)2(4,4'-bipy)] units. The Mo-O chain contains distorted [MoO(6)] octahedra connected through corner-sharing oxygen atoms into infinite chains along the c direction and each chain is located in the channel formed by four adjacent crossing chains of [Cu(4,4'-bipy)(H2O)](n)(2n+). The crystal shows weak conductivity through Mo-O chain along the c direction and insulating property along either a or b direction. Furthermore, a crystalline bimetallic oxide, CuMo3O10, forms when the title compound undergoes thermal treatment in N(2) atmosphere after the complete removal of the ligands.     

One- and two-dimensional silver and zinc uranyl phosphates containing bipyridyl ligands

The reaction of AgCN with UO2, 4,4'-bipy, and phosphoric acid in water at 160 degrees C under autogeneously generated pressure results in the formation of [Ag(4,4'-bipy)]2[(UO2)2H3(PO4)3] (AgUP-1). Ag(2,2'-bipy)(UO2)2(HPO4)(PO4) (AgUP-2) has been prepared from the hydrothermal reaction (at 180 degrees C) of KAg(CN)2 with UO2(C2H3O2)2.2H2O and 2,2'-bipy. [Zn(2,2'-bipy)]2[UO2(HPO4)3] (ZnUP-1) was isolated from the hydrothermal reaction of UO2, 2,2'-bipyridyl, Zn(CN)2, and H3PO4. Single crystal X-ray diffraction experiments reveal that the structure of AgUP-1 consists of 2infinity[(UO2)2H3(PO4)3]2- expanded autunite-like layers in the [ac] plane, separated by 1infinity[Ag(4,4'-bipy)]+ chains of two-coordinate Ag+ bridged by 4,4'-bipy. The structure of AgUP-2 is composed of chains of edge-sharing UO7 pentagonal bipyramids that are linked by phosphate anions into 2infinity[(UO2)2(HPO4)(PO4)]1- sheets with the beta-uranophane topology that extend in the [ab] plane. Both sides of the sheets are decorated by [Ag(2,2'-bipy)]+ units, where the Ag+ cations are found in distorted trigonal planar environments. The structure of ZnUP-1 is 1D and consists of UO7 pentagonal bipyramids that are connected by phosphate anions that also bind four-coordinate zinc(II) to the periphery of the chains and five-coordinate zinc within the chains. Intense fluorescence from these compounds was observed.