Synthesis and Structural Characterization of Mono-and Di-nuclear Zinc（ Ⅱ ） Coordination Compounds of Triphenylphosphoniopropionate

IntroductionThe coordination chemistry of zinc(Ⅱ)has beensubjected to extensive study in the past decades owingto its importance in life science[1].It has been foundthat zinc(Ⅱ)ions are crucially involved in the activesites of over300metalloenzymes and their role is notonly confined to catalysis and gene expression.Further-more,the presence of zinc(Ⅱ)helps to stabilize thetertiary and quaternary structures of proteins and nucle-ic acids[2—4].Like cadmium(Ⅱ),zinc(Ⅱ)is clearly amongthose m…     

Synthesis and Structural Characterization of Co(Ⅱ) Coordination Polymer [Co(-phth)(imi_)2]_n

1 INTRODUCTION The polymeric metal complexes with extended structures are of great interest because of their useful chemical or physical properties[1]. Due to the noticeable fact that the aromatic polycarboxylate can provide versatile coordination mode and the non-coplanar structure of the carboxylate groups and the benzene rings, a lot of efforts in this field have been particularly directed to the preparation of aromatic polycarboxylate (such as phthalate, tere- phthalate and isophthal…     

Synthesis and Luminescence Properties of Three High-dimensional Coordination Polymers:Zn(Ⅱ) with Imidazole or Benzimidazole Ligand

A novel 2D coordination polymer [Zn2(bim)4]n(1)(Hbim=benzimidazole) based on dihydrated-[N,N'-bis(2-aminophenl)-oxalamide](L1·2H2O) with zinc nitrate has been synthesized.Previously we have synthe-sized complexes [In2Zn3(im)12]n(2)(Him= imidazole) and [Zn(im)2]n(3) successfully.In complex 1,each Zn(Ⅱ) coor-dinated with four ligands adopts a distorted tetrahedron coordination mode,and the 2D grid structure is built by the Zn(bim)4 as the secondary building unit(SBU).The luminescence properties of the three c...     

Synthesis, Characterization and Crystal Structure of a Three-dimensional Coordination Polymer {[Cd(1,5-nds)(Him)2(H2O)]·2H2O}n

A novel cadmium(Ⅱ) coordination polymer {[Cd(1,5-nds)(Him)2(H2O)]·2H2O}n (1,5-nds = naphthalene-1,5-disulfonate and Him = imidazole) was synthesized based on the reaction of cadmium oxide and 1,5-naphthalenedisulfonic acid firstly, and then mixed with imidazole in methanol medium. Its structure was characterized by elemental analysis, IR and TGA, respectively. The crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P, with a = 8.5420(10), b = 10.2570(10), c = 13.361(2)(A), α = 100.704 (2), β = 100.195(2), γ = 108.873(3)°, C16H20Cd N4O9S2, Mr = 588.91, V = 1.0524(2) nm3, Dc = 1.858 g/cm3, Z = 2, F(000) = 592, μ= 1.294 mm-1, R = 0.0397 and wR = 0.1007 for 3180 observed reflections (I > 2σ(I)). Structural analysis shows that the cadmiun atom is coordinated with four oxygen atoms from three 1,5-nds and one water molecule together with two nitrogen atoms from two imidazoles, giving a distorted octahedral coordination geometry. The molecules are linked to form a two-dimensional coordination polymer based on bridging ligands of naphthalene-1,5-disulfonate anions, the sheets of which are then interacted via hydrogen bonds, leading to a three-dimensional network structure.     

Syntheses and Crystal Structures of Two New Zinc(Ⅱ)Nitroxide Radical Complexes Bridged by Isophthalate

Two novel complexes [Zn(NIT3-py)(ip)]n 1 and [Zn(im3-py)(ip)]n 2 (NIT3-py =2-(3"-pyridyl)-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide, im3-py = 2-(3'-pyridyl)-4,4,5,5-te-tramethylimidazoline-1-oxyl, ip = isophthalate) have been synthesized and structurally determinedby X-ray diffraction.Crystal data for 1: C32H36N6O8Zn, Mr= 698.04, monoclinic, space group C with a = 23.600(3), b = 10.2073(12), c = 13.4027(16)(A), β= 92.586(2)°, V = 3225.3(7) (A)3, Dc=1.438 g/cm3, F(000) = 1456,μ(MoKα) = 0.822 mm-1, Z = 4, the final R = 0.0390 and wR = 0.1032 for 6037 independent reflections with Rint=0.0214.Crystal data for 2: C32H36N6O6Zn, Mr = 666.04,monoclinic, space group C2/c with a = 24.434(4), b = 13.543(2), c = 10.2379(16)(A), β= 109.024(2)°,V= 3202.8(9)(A)3, Dc= 1.381 g/cm3, F(000) = 1392,μ(MoKα) = 0.820 mm-1, Z= 4,the final R = 0.0304 and wR = 0.0658 for 2833 independent reflections with Rint = 0.0307.X-ray analysis reveals that both Zn(Ⅱ) ions are four-coordinated by two pyridyl-N atoms from nitroxide radicals and two carboxylate oxygen atoms to form distorted tetrahedral geometries.Each iso-phthalate dianion binds two Zn(Ⅱ) ions in a monodentate mode, leading to a 1-D chain structure.     

A New One-dimensional Dicyanamide Bridged Zinc(Ⅱ) Complex Containing Nitronyl Nitroxide Radicals: Synthesis,Crystal Structure and Magnetic Properties

A new one-dimensional dicyanamide bridged zinc(Ⅱ) complex containing nitronyl nitroxide radicals [Zn(NO3)(NIT-1'-MeBzim)(dca)]n·(H2O)n (NIT-1'-MeBzIm = 2-{2'-[(1'-me-thyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoine-1-oxyl-3-oxide, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in trielinic, space group P1, with a = 7,428(3), b = 9.839(3), c = 16.708(6) A, а = 93.270(4), β= 101.642(4),γ= 100.632(4)°, C17.5H21N8O5.5Zn, Mr = 496.79, V= 1169.7(7) A3, Dc = 1.411 g/cm3,μ(MoKa) = 1.096 mm-1, Z = 2, F(000) = 512, R = 0.0583 and wR = 0.1663 for 4295 observed reflections with I > 2σ(I). X-ray analysis reveals that the zinc(Ⅱ) ion is six-coordinated with a distorted oetahedral geometry. These units develop as 1D species where dieyanamide ligands bridge zine(Ⅱ) ions. In addition, molecules are linked by π-π piling interactions to form 1-D double-chains. Magnetic investigation indicates that the weak intramoleeular interactions are antiferromagnetic with J = -0.27 cm-1, where the spin Hamitonian is defined as H = -2 ∑ijJijSiS within the complex.     

Synthesis and Crystal Structure of Zn(Ⅱ) Complex with Tridentate Ligand N-(2-Hydroxy-1-naphthylidene)-L-serine

A new Zn(Ⅱ) complex, [Zn(L)2(H2O)2], where H2L = N-(2-hydroxy-l-naphthylidene)-L-serine, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 13.669(2), b = 6.4657(9), c =31.463(5) (A), β = 98.010(2)°, V = 2753.6(7) (A)3, Z = 8, Mr = 358.64, Dc = 1.730 g/cm3, F(000) =1472,μ(MoKa) = 1.814 mm-1, the final R = 0.0355 and wR = 0.0706. The Zn(Ⅱ) atom adopts a square-pyramidal geometry coordinated by the tridentate ligand and two water molecules.Intermolecular hydrogen bonds link the complex molecules into a two-dimensional layer.     

A Two-dimensional Anthracene-9,10-dicarboxylate Zinc(Ⅱ) Coordination Polymer Based on Binuclear [Zn_2Cl_2] Nodes: Synthesis,Characterization and Luminescent Properties

A two-dimensional(2D) 44 topological ZnⅡ coordination polymer {[Zn2Cl2(L)(4bpy)2]}∞(H2L = anthracene-9,10-dicarboxylic acid, 4bpy = 4,4ˊ-bipyridine) based on binuclear [Zn2Cl2] nodes has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction analysis. Moreover, the luminescent properties of the correspon- ding compound have been briefly investigated.     

Structure and Magnetic Properties of a Bipyridine-bridged One-dimensional Ni(Ⅱ) Coordination Polymer

A polymer, [NiL(bipy)·2H2O]n(1, bipy = 4,4ˊ-bipyridine), has been acquired by the reaction of Ni(OAc)2·4H2O with N,Nˊ-bis(2-hydroxyl-5-fluorobenzyl)-2-hydrxylpropane dii- mine in the presence of 4,4ˊ-bipyridine. X-ray crystallographic analysis shows that it is comprised of a mononuclear Ni(Ⅱ) complex [NiL] linked by 4,4ˊ-bipyridine. Its crystal crystallizes in the orthorhombic system, space group C2/c with a = 22.595(3), b = 18.395(2), c = 15.434(2) , V = 6155(1)3, Dc = 1.259 g/cm-3, Z = 8, Mr = 583.23, F(000) = 2416.0, μ(MoKa) = 0.681 mm-1, S = 1.049, R = 0.0512 and wR = 0.1108 for 6032 observed reflections(I 2σ(I)). There are water hexamers in the complex. A weak overall ferromagnetic behavior has been evaluated by Curie-Weiss rule and by the formula of alternating ferro-ferromagnetic coupling in one-dimensional Ni(Ⅱ) chain, which gives g = 2.005(1) and J1 = 0.31(3) cm-1.     

Synthesis,Structure and Luminescent Property of a 2D Cd(Ⅱ) Coordination Polymer Based on Mixed-ligands of 1,3-Bis(imidazol)propane and Pyridine-3,5-dicarboxylic Acid

A new Cd(Ⅱ) coordination polymer, namely, [Cd(1,3-bip)(3,5-pdc)]n(1,3-bip =1,3-bis(imidazol)propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis,powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178(7), b = 1.72502(12), c = 1.41635(6) nm, β =92.653(4)o, V = 3.4212(3) nm3, Z = 4, C316H15 Cd N5O4, Mr = 453.73, Dc = 1.762 g/cm, F(000) =1808, μ = 1.310 mm-1, R = 0.0899 and w R = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd(Ⅱ) ions and each Cd(Ⅱ) attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.     

Synthesis and Crystal Structure of a New Cadmium（Ⅱ） Coordination Polymer with Ethylenediaminetetraacetic Acid

A new cadmium(Ⅱ) coordination polymer,namely,[KCd2(edta)I]n(1,H4edta = ethylenediaminetetraacetic acid),has been prepared and structurally characterized by single-crystal X-ray diffraction.Crystallographic data for 1:C10H12Cd2IKN2O8,Mr = 679.02,monoclinic,space group P21/n,a = 9.870(5),b = 8.989(4),c = 19.082(10) ,β = 104.581(10)o,V = 1638.5(13) 3,Z = 4,Dc = 2.753 g/cm3,μ = 4.776 mm-1,F(000) = 1272,the final R = 0.0473 and wR = 0.1311 for 2846 observed reflections with I > 2σ(I).Polymer 1 features a 2-D layered structure,in which each edta4-ligand chelates/bridges five adjacent six-/seven-coordinated Cd(Ⅱ) centers with all ten donors(eight oxygen and two nitrogen) involved with coordination.Additional iodide I-ions as counterions are bound to the Cd(Ⅱ) centers in a terminal mode and the potassium K+ ions are located in the layers and surrounded by O and I atoms from neighboring environment.The thermal stability of 1 has been discussed.     

Synthesis, Characterization and Crystal Structure Determination of a Thiocyanato Bridged One-dimensional Polymeric Complex of Cadmium(Ⅱ)

A new one-dimensional polymeric complex [Cd(SCN)2(H2O)]L (L = N,N?-bis(furan- 2-ylmethylene)hydrazine) has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, pace group P1 with a = 5.9268(8), b = 10.8678(15), c = 13.3671(19) , α = 109.295(2), β = 95.092(2), γ = 97.8580(10)°, V = 796.70(19) 3, Z = 2, C12H10CdN4O3S2, Mr = 434.76, μ = 1.648 mm–1, Dc = 1.812 g/cm3, F(000) = 428, R = 0.0308 and wR = 0.0769. The crystal structure reveals that the structure of [Cd(SCN)2(H2O)]n features di-μ-1,3-thiocyante bridges and 1D chains. The octahedrally coordinated Cd atom is surrounded by one oxygen atom from water molecule, three S atoms and two Natoms from five di-μ-1,3 thiocyanato bridges. The Cd atoms are connected by two di-μ-1,3 thiocyanato bridges with the Cd(1)…Cd(1A) separation of 4.239(1)  and Cd(1)…Cd(1B) of 5.852(1). In addition, the one-dimensional straight chain structure is further connected by multiform intermolecular N-H…O hydrogen bonds and π…π interactions to form a three-dimensional supramolecular structure.     

Synthesis and Crystal Structure of a Mononuclear Zn(Ⅱ) Complex with Tridentate Schiff Base, Zn(C12H18N2O)(NCS)2

The title complex Zn(HL)(NCS)2 (C14H18N4OS2Zn, Mr = 387.81, HL = N-(3-dimethyl-aminopropyl)-salicylaldimine) has been synthesized by the reaction of ZnSO4·7H2O with the Schiff base N-(3-dimethylaminopropyl)-salicylaldimine derived from the condensation reaction of 3-dimethylamino-1-propylamine with salicyladehyde. It crystallizes in the monoclinic system, space group P21/n with a = 9.8360(8), b = 14.930(1), c = 12.277(1) (A), β= 101.455(2)°, V= 1767.0(3) (A)3,Z = 4, F(000) = 800, Dc = 1.458 g/cm3 and μ(MoKα) = 1.631 mm-1. The structure was refined to R = 0.0463 and wR = 0.1065 for 2681 observed reflections (I ＞ 2σ(Ⅰ)). Crystal analyses revealed that the Zn(Ⅱ) atom is coordinated by two nitrogen atoms of two NCS-, and an oxygen atom as well as a nitrogen atom of amine from the neutral Schiff base ligand of N-(3-dimethyl-aminopropyl)-salicylaldimine to give a distorted tetrahedral geometry.     

Synthesis and Properties of u-Oxamido Heterobinuclear Cu(Ⅱ)-Co(Ⅱ) Complexes

Three heterobinuclear complexes were synthesized, namely [Cu (oxpn) Co (L)2] (ClO4)2·xH2O(L= 2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen) , and 5-nitro-1, 10-phenanthroline (NO2-phen)), where oxpn represents N, N'-bis(3-aminopropyl) oxam-ido. Based on 1R, elemental analysis, conductivity measurement and electronic spectra, these complexes were characterized by an extended oxamido-bridged structure with Cu(Ⅱ) in a planar environment and Co(Ⅱ) in a octahedral environment. The symmetry of the cation is very close to C2v.The complexes were also characterized with variable temperature (4~300K) magnetic susceptibility, and the data were fit for the susceptibility equation derived from spin Hamilton, H= -2JS1.S2-DSx12 by least square strategy. The exchange integral, J, was found to be -22.36 cm-1 (for bpy);-15.45 cm-1 (for phen); -19. 10cm-1(for NO2-phen), indicating that there is a weak antiferromagnetic spin-exchange interaction between the metal ions.     

Blue Luminescent Zinc(Ⅱ)- and Cadmium(Ⅱ)-1,4-phenylenediacetate Complexes

Two mixed-ligand polymeric complexes formulated as {[Zn(pda)(bpy)]·0.5H2O}n (pdathermally synthesized. Single-crystal X-ray diffraction analyses reveal that the structures of complexes 1 and 2 possess similar one-dimensional zigzag chains. Crystal data for compound 1: monoclinic, space group P21/c, a = 15.965(2), b = 8.305(1), c = 14.856(2) (A),β= 1 1 1.048(2)°, Mr = 422.73, V= 1838.2(4) A3, Z= 4, Dc = 1.528 g/cm3, μ = 1.368 mm-1, F(000) = 868, the final R = 0.0783 and wR= 0.1469 (w=1/[σ2(Fo2) + (0.035 1p)2+ 8.0014P], where P = (Fo2+ 2Fc2)/3) based on 2025 observed reflections with I ＞ 2σ(I); and those for compound 2: monoclinic, space group C2/c, a = 29.921 (7), b= 8.5400(17), c = 15.320(3) (A),β= 99.59(3)°, Mr = 487.75, V = 3859.9(14) A3, Z = 8, Dc = 1.668g/cm3, μ = 1.169 mm-1, F(000) = 1936, the final R = 0.0723 and wR = 0.1612 (w = 1/[σ32(Fo2 ) +(0.0681p)2+ 55.9577P], where P = (Fo2+ 2Fc2)/3) based on 2130 observed reflections with I ＞ 2σ(I).Fluorescent analyses show that both complexes exhibit intense blue luminescence (λmax = 485 nm for 1and 475 nm for 2) upon excitation at 330 nm.     

Mass spectrometry assisted assignments of binding and cleavage sites of Zn(Ⅱ)complex towards oxidized insulin B chain

The electrospray ionization mass spectrometry investigation showed that the binding sites of [ZnL]2+, where L is 2-[bis(2-aminoethyl)aminolethanol, with oxidized insulin B chain are Phe1, His5 and Arg22, which lead to the selective cleavages of the peptide bonds at Phe1-Val2, His5-Leu6, Glu21-Arg22, and Arg22-Gly23 of oxidized insulin B chain.     

Synthesis and Crystal Structure of a Palladium(Ⅱ)Coordination Polymer [Na2Pd(2,6-pydc)2(H2O)6]n

A novel coordination polymer [Na2Pd(2,6-pydc)2(H2O)6]n (2,6-H2pyde = 2,6-pyri-dinedicarboxylie acid) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinie system, space group P21/c,with a = 11.962(2), b = 6.5552(13), c = 12.673(3) A, β = 91.72(3)°, V= 993.3(3) A3,Z = 2, Mr=590.68, Dc = 1.975 g/cm3,μ=1.059 mm-1, F(000) = 592, the final R = 0.0211 and wR = 0.0454. In the crystal the Pd(Ⅱ) ion adopts a distorted four-coordinated square-planar geometry and bonds to two bidentate 2,6-pyridinedicarboxylate molecules through caronyl oxygen and pyridine nitrogen atoms. The title complex exhibits a novel three-dimensional network structure.     

Two Novel Cobalt(Ⅱ)/nickel(Ⅱ) Metal-organic Coordination Polymers Based on Flexible Polycarboxylic Acids and Rigid Bis(imidazole) Mix Ligands

Two novel metal-organic coordination compounds, [Co2(OH)(chdc)1.5(bibp)]n(1) and [Ni(chdc)(bib)]n·2nH2O(2, H2chdc=1,4-cyclohexanedicarboxylic acid, bibp=4,4’-bis(1-imidazolyl)biphenyl, bib=1,4-bis(1-imidazolyl)benzene), were synthesized and characterized. Compound 1 crystallizes in monoclinic system, space group PI with a=10.591(3), b=11.146(3), c=12.264(3) ?, α=89.009(6), β=88.397(4), γ=87.823(3)°, V=1446.0(6) ?3, Dc=1.554 g/cm3, C30H30Co2N4O7, Mr=676.44, F(000)=696, μ(MoKα)=1.202 mm-1, Z=2, R=0.0278 and wR=0.0718. In 1, it contains an interesting tetranuclear Co(Ⅱ) cluster. The neighboring {Co4} clusters are linked by chdc2-ligands to generate a 2D network. The bibp ligands connect adjacent layers to form an open 3 D metal-organic framework. Compound 2 crystallizes in monoclinic system, space group P21/n with a=8.8110(1), b=19.369(1), c=12.7379(4) ?, β=102.952(5)o, V=2118.5(2) ?3, Dc=1.490 g/cm3, C20H24N4NiO6, Mr=475.14, F(000)=992, μ(MoKα)=0.961 mm-1, Z=4, R=0.0306 and wR=0.0738. In 2, each deprotonated chdc 2-ligand links two Ni(Ⅱ) atoms to generate a 1 D chain along the a axis. The adjacent chains are further connected by bib ligands to build up an interesting two-dimensional network. Compound 1 shows antiferromagnetic property.     

Synthesis,Characterization and Thermostability of a Novel Pb(Ⅱ) Coordination Polymer with Mixed Ligands

A novel mixed-ligand coordination polymer [Pb(phen)(NNDS)(H2O)]n·n H2O(1) was obtained from the reaction of 1,10-phenanthroine(phen), Pb(OAc)2 and sodium 1-nitroso-2-naphthol-3,6-disulfonate(Na2NNDS) in a mixed solvent. The complex was characterized by elemental analysis, IR and X-ray single-crystal diffraction. Crystal data for 1: monoclinic, space group P21/c, a = 11.5835(9), b = 14.6334(11), c = 13.9030(11) ?, β = 98.4180(10)o, V = 2331.3(3) ?3, Z = 4, Mr = 754.70, Dc = 2.150 mg/m3, μ = 7.483 mm-1, F(000) = 1456, the final R = 0.0430 and w R = 0.0841 for 4221 observed reflections with I 2σ(I). The Pb(II) center is coordinated by six O and two N atoms showing a distorted dodecahedron configuration. The multidentate ligand of NNDS dianion exhibits peculiar coordination mode, and the two O atoms of two sulfonate anions bridge two Pb(II) cations into a dimer, and the O atom of nitroso group links the other dimer into 2D sheets extending in the [011] plane. There exist significant π-π stacking interactions between adjacent phen and NNDS. The 3D network is formed by 2D sheets interlinked by hydrogen bonds and π-π stacking interactions. The thermostability of 1 was investigated by TG and DSC.     

Synthesis, Characterization and Cytotoxicity of Ammine/Methylamine Platinum(Ⅱ) Complexes with Carboxylates

Seven novel platinum (Ⅱ) complexes [Pt (Ⅱ) (NH3) (CH3NH2) X2] (Ⅰ -Ⅶ) (X: CH3COO- ,CH2 ClCOO - , CHCl2COO -, C6H5-COO - , p-CH3O-C6H4 -COO - , p-NH2-C6 H4 -COO - , p-NO2 -C6 H4 -COO-) were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis,IR, UV, and 1 H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence: cisplatin ＞Ⅳ＞Ⅴ＞Ⅵ＞Ⅶ＞Ⅰ＞Ⅱ＞Ⅲ. Moreover, the complexes(Ⅰ -Ⅶ) display substantially greater activities against EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.