Synthesis,Crystal Structure and Norbornene Polymerization of a Palladium(Ⅱ) Complex Based on Phenoxyimine Ligand

The title complex N,O-bis{2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol}-palladium(II)(C_(80)H_(64)N_2O_2 Pd) has been synthesized by the reaction of 2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol with Pd(CH_3COO)_2, and characterized by IR spectrum and elemental analysis. The spatial structure of the complex has been verified by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group P21/n with a = 13.492(3), b = 16.924(3), c = 14.135(3) ?, β = 97.84(3)°, V = 3197.4(11) ?~3, C_(80)H_(64)N_2O_2 Pd, Mr = 1191.73, Z = 2, Dc = 1.238 Mg/m~3, μ = 0.339 mm~(-1), F(000) = 1240, T = 293(2) K, the final R = 0.0593 and wR = 0.1192(I 2s(I)). The compound showed excellent catalytic activity up to 1.130 × 10~7 g of PNB(mol of Pd)~(-1)h~(-1) for the addition polymerization of norbornene by using methylaluminoxane(MAO) as a cocatalyst.     

Synthesis,Crystal Structure and Luminescent Property of a Zn(Ⅱ) Complex Based on 4-Imidazole-carboxylate Ligand

A new complex, [Zn(L)_2](1), has been hydrothermally prepared by the reaction of ZnSO_4·7H_2O with 2-(1H-imidazol-4-yl)benzoic acid(HL) incorporating 4-imidazolyl and carboxylate functional groups, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and powder X-ray diffraction(PXRD). Complex 1 crystallizes in monoclinic, space group C2/c with a = 9.8349(9), b = 7.4947(7), c = 24.104(2) ?, β = 92.889(2)o, V = 1774.4(3) ?~3, Z = 4, C_(20)H_(14)N_4O_4 Zn, M_r = 439.72, D_c = 1.646 g/cm~3, μ = 1.422 mm~(-1), S = 1.003, F(000) = 896, the final R = 0.0395 and wR = 0.0874 for 11386 observed reflections(I 2σ(I)). Single-crystal X-ray structural analysis reveals that complex 1 features a two-dimensional(2D) framework with 6~3-hcb topology. Moreover, the photoluminescent property of 1 was also discussed.     

Synthesis,Structure and Catalytic Activity of a Manganese(Ⅲ) Complex Based on 2-(2-Hydroxyphenyl)-5,6-dichlorobenzimidazole Ligands

A new ligand, 2-(2-hydroxyphenyl)-5,6-dichlorobenzimidazole, H2pbmCl2(1), and a novel MnIII complex, [MnIII(HpbmCl2)(pbmCl2)(DMF)2](2),(DMF = N,N-dimethylformamide), have been synthesized and characterized. The crystal of compound 1(C13H8Cl2N2O, Mr = 279.12) belongs to the monoclinic system, space group P21 with a = 3.770(5), b = 25.20(3), c = 5.865(7) , = 92.727(17)o, V = 556.6(12) 3, Z = 2, Dc = 1.665 g/cm3, S = 1.137, μ= 0.568 mm-1, F(000) = 284, the final R = 0.0876 and wR = 0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O–H group of phenol and N atom of imidazole. H2pbmCl2(1) molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds(N–H···O and C–H···Cl). The crystal of complex 2(C32H27Cl4MnN6O4, Mr = 756.34) belongs to the monoclinic system, space group P21/c with a = 19.043(10), b = 10.808(5), c = 18.704(11), = 115.540(6)o, V = 3473(3) 3, Z = 4, Dc = 1.446 g/cm3, S = 1.3, μ = 0.733 mm-1, F(000) = 1544, the final R = 0.1219 and wR = 0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The [MnIII(HpbmCl2)(pbmCl2)(DMF)2] molecules are arranged into a three-dimensional structure through hydrogen bonds(N–H···N, C–H···N and C–H···Cl) and weak π···πinteractions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.     

Synthesis,Structure and Norbornene Polymerization Activity of a Novel Palladium(Ⅱ) Complex with N,OBis{1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} Ligand

The title complex bis{1-[[(3-methyl-pyridin-2-yl) amino] methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} palladium(C_(42)H_(56)O_2N_4Pd) has been synthesized by the reaction of 1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol with Pd(OAc)_2, and was characterized by IR and elemental analyses(C, H, N). Single-crystal X-ray diffraction analysis of the complex revealed an almost parallelogram geometry of the metal center, space group P1 with a = 12.3870(13), b = 12.9673(12), c = 14.3998(4) ?, α = 67.53(2), β = 75.34(2), γ = 86.89(3)°, V = 2065.5(3) ?~3, M_r = 773.32, Z = 2, D_c = 1.243 g/cm~3, μ = 0.489 mm~(-1), F(000) = 816, the final R = 0.0649 and wR = 0.1567. The compound was investigated for the catalytic behavior towards norbornene(NB) vinyl addition polymerization. And the complex exhibits high catalytic activities up to 1.668 × 10~7 g of PNB(mol of Pd)~(-1) h~(-1) with high monomer conversion using methylaluminoxane(MAO) as the cocatalyst.     

Synthesis and Crystal Structure of a Copper(Ⅱ)Complex with Funnel-like Ligand Based on Calix[6]arene

The preparation method of a funnel like ligand derived from calix[6]arene and tris(2-pyridyl-methyl)anime has been improved.The Cu(Ⅱ)complex was obtained and ch...     

Synthesis,Crystal Structure and Electrochemistry Properties of a Cobalt(Ⅱ) Complex Based on Asymmetry Schiff Base Ligand

A new cobalt(II) complex [Co(NO2-salen)2]·1.5H2O containing mono acetalization Schiff base ligand(NO2-salen = N-5-nitro-salicylideneamino ethanato) has been prepared through one-pot template condensation, and has been structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It is formulated as C18H23CoN6O7.5, crystallizes in the hexagonal system, space group of R-3c with α = 25.895(18), b = 25.895(18), c = 35.075(6), γ = 120o, V = 20368(3) and Z = 36. The ligand of 5-nitrosalicylaldehyde-ethylene-diamine takes unusual mono asymmetry mode. The Co(II) ion exhibits a coordination number of six, and assumes a distorted octahedral geometry with a N2O4 donor set. The neutral monomeric units of [Co(NO2-salen)2]·1.5H2O are linked into a one-dimensional(1D) structure via the intermolecular hydrogen bonds and weak π-π stacking interactions. Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are irreversible in nature.     

Synthesis and Crystal Structure of 2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol-copper(Ⅱ)

2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol-copper(Ⅱ) has been designed and synthesized.The structure was determined by UV,IR and single-crystal X-ray study.The title complex crystallizes in the triclinic system,space group P1 with a=6.6090(13),b=10.377(2),c=12.550(3),α=113.29(3),β=93.84(3),γ=98.31(3)°,V=774.9(3)3,Dc=2.215g/cm3,C26H30CuO4N4I4,Mr=1033.68,F(000)=487,μ=4.726 mm-1,Z=1,the final R=0.0563 and wR=0.1475 for 2101 observed reflections(I2σ(I)).The central copper(Ⅱ) is four-coordinated by two nitrogen atoms and two oxygen atoms from two 3,5-diiodosalicylaldehyde-2-morpholinoethylamine Schiff bases.The complex is linked into a column by π-π stacking interaction.The complex was assayed for antibacterial activities against three Gram positive bacterial strains(B.subtilis,S.aureus and S.faecalis) and three Gram negative bacterial strains(E.coli,P.aeruginosa and E.cloacae) by MTT method.Fortunately,the title complex shows potent antibacterial activity against these six bacterial strains.     

Synthesis,Crystal Structure and Antitumor Activity of a New Zn(Ⅱ) Complex Based on N-Acetyl-L-phenylalanine and 1,10-Phenanthroline

A new Zn(Ⅱ) complex, [Zn(L)_2(phen)(H_2O)](1, HL = N-acetyl-L-phenylalanine, phen = 1,10-phenanthroline) has been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction analysis. The Zn(Ⅱ) complex belongs to monoclinic, space group P21 with a = 12.6749(13), b = 5.5965(6), c = 22.985(2) ?, β = 104.296(2)°, V = 1580.0(3) ?~3, Z = 2, M_r = 676.02, D_c = 1.421 μg·m~(-3), μ = 0.833 mm~(-1), F(000) = 704, and the final R = 0.0460, wR = 0.0899 for 4422 observed reflections with I 2σ(I). The molecules form a 1D chained structure by hydrogen bonds. The antitumor activities of Zn(Ⅱ) complex against human hepatoma SMMC-7721 cells, human lung adenocarcinoma A549 cells and human colon carcinoma WiDr cells have also been investigated.     

Synthesis,Crystal Structure and Antitumor Activity of a Novel Zn(Ⅱ) Complex with 2-(Nicotinoyloxy)acetic Acid Ligand

A novel Zn(Ⅱ) complex, [ZnL_2(H_2O)_4]·H_2O(1, HL = 2-(nicotinoyloxy)acetic acid), was synthesized using Zn(OAc)_2·2H_2O and 2-(nicotinoyloxy)acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn(Ⅱ) atom is six-coordinated with two N atoms from two different 2-(nicotinoyloxy)acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-(nicotinoyloxy)acetic acid ligand and its Zn(Ⅱ) complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.     

Synthesis,Crystal Structure and Luminescence Properties of a Cadmium(Ⅱ) Complex Based on 2-Hydroxy-6-methylisonicotinic Acid

A new cadmium(Ⅱ) complex[Cd(Hminic)(IP)]_n(1,Hminic = 2-hydroxy-6-methylisonicotinic acid,IP = imidazo[4,5-f]-l,10-phenanthroline),has been synthesized by the reaction of a Hminic and auxiliary N-containing ligands with Cd(Ⅱ) ion under hydrothermal conditions.The complex was studied by elemental analysis,IR spectroscopy and X-ray crystallography.It is formulated as C_(20)H_(13)CdN_5O_3,crystallizes in monoclinic system,space group C2/c with α=9.6764(8),b = 26.767(2),c = 14.1332(11) A and β= 97.4510(10)°.V= 3629.7(5) A~3,Z = 8,Mr=483.75,D_c = 1.770 g/cm~3,F(000) = 1484 and μ= 1.237 mm~(-1).The final refinement gave R = 0.0309 and wR = 0.0703 for 4151 reflections with I 2σ(I).In the structure of 1,two Cd(Ⅱ) atoms are joined by a pair of μ_2-hydroxyl oxygen atoms giving rise to a dinuclear Cd(Ⅱ) unit which is bridged by Hminic linkers to form a 1D ladder-like polymer chain.The chelating ligand IP coordinated to the Cd(Ⅱ) atom,and alternately attached to both sides of the ladder-like polymer chain.Adjacent chains are further bound together by strong intermolecular hydrogen bonds and face-to-face π…πinteractions,resulting in the formation of a 3D supramolecular architecture.Furthermore,the thermal stability and luminescent properties of this complex and the free ligands have been investigated.     

Synthesis,Crystal Structure and Catalytic Activity Palladium (Ⅱ) Complexes Containing Bulky Azole Ligands

Bulky azole ligands in combination with PdCl_2 provide three new palladium(II) complexes. All these complexes, as pre-catalysts, have high catalytic efficiency for the Suzuki-Miyaura cross-coupling reactions of sterically hindered aryl chlorides and good to high yields are obtained with low catalysts loadings(0.1 mol%) under mild conditions in air.     

Synthesis, Crystal Structure and Antimicrobial Activity of a Novel Ni(Ⅱ) Complex

A new nickel(Ⅱ) complex, C34H38N8NiO4, has been prepared and charac-terized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 11.715(5), b = 12.328(5), c =11.113(5) A, β= 92.589(5)°, Z = 2, Dc = 1.411 g/cm3, μ = 0.658 mm-1, the final R = 0.0427 and wR = 0.1099 for 2229 observed reflections with Ⅰ> 2σ(Ⅰ). The complex is a centrosymmetric plane in which nickel(Ⅱ) is coordinated in a regular octahedron to the ligand phenytoin through the nitrogen atoms of ethylenediamine, imine and amine. The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method, and found to be active against the four test bacterial organisms. Preliminary screening for antimicrobial activities showed that the title complex is quite active against standard strains of Salmonella species, Staphylococcus aureus, Bacillus pumilus and Eschierichia coli.     

Studies on the Crystal Structure and Photoluminescence of a Mercury(Ⅱ)Complex Based on a Novel Pyridine Ligand

<正>A novel mercury(n)complex HgL_2Br_2 was prepared from HgBr_2 and the organic ligand 2-(N-methyl-N-(4-((E)-2-(pyridine-4-yl)vinyl)phenyl)amino)ethanol(L).The ligand was synthesized and then characterized by FT-IR spectroscopy,~1H NMR,mass spectrum and elemental analysis,while the single-crystal diffraction data of the complex were collected on a Siemens Smart CCD diffractometer.The complex crystallizes in triclinic space group P_1~-with a=5.367(5),b= 12.466(5),c=23.945(5)(?),α=90.812(5),β=96.318(4),γ=96.093(5)°,Z=2,D_c=1.817g·cm~(-3),μ=7.395 mm~(-1),S=0.825,and the final R=0.0396.The Hg(Ⅱ)ion in the distorted tetrahedral mercury(Ⅱ)complex C_(32)H_(36)HgBr_2N_4O_2 is coordinated by two N atoms from the two ligands together with two bromide ions.Solid-state emission of the ligand and its complex has been investigated at room temperature.     

Synthesis,Crystal Structure and DNA-Binding Property of a New Cu(Ⅱ) Complex Based on 4-(Trifluoro-methyl)nicotinic Acid

A new complex[Cu_1.5(tfc)₃(H₂O)₄]·3H₂O (1,Htfc=4-(trifluoro-methyl) nicotinic acid) has been synthesized and characterized by X-ray single-crystal diffraction,elemental analysis,IR spectra and thermogravimetric analysis.1 belongs to orthorhombic system,space group Pccn with a=44.507(2),b=10.7710(6),c=11.7544(7)?,V=5634.9(6)?³,Z=1,D_c=1.803 mg·cm^-3,F(000)=3068,μ=1.266 mm^-1,the final R=0.0488and w R=0....     

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ) Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper(Ⅱ) complex with tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate(ampy) was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper(II) complex with ampy, [Cu(ampy)Cl2](1), was formed irrespective of the metal-to-ligand molar ratios([Cu2+]:[ampy] = 0.5:1, 1:1, and 2:1) as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343(2), b = 18.928(3), c = 20.058(4) ?, V = 4686.1(14) ?3, Z = 8, Dc = 1.3349(4) g/cm~3, F(000) = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the central copper(II) ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H···Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory(DFT/B3LYP) method with the basis sets(6-31+G(d,p) for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively). The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital(NBO) analysis and frontier molecular orbitals(FMOs) analysis were investigated at the same level.     

Hydrothermal Synthesis,Crystal Structure and Antimicrobial Activity of a New Ni(Ⅱ) Complex

The title complex [NiL]·H2O(C20H24N2NiO5,L = paeonol-ehylenediamine) was synthesized by the hydrothermal method and characterized by IR,cyclic voltammetry and X-ray single-crystal diffraction.The complex belongs to the monoclinic system,space group P21/c with a=13.4361(13),b=7.3290(10),c=20.981(2),β=109.244°,V=1950.6(4)3,Z=4,F(000)=904,Dc=1.468 g/cm3,μ(MoKα)=1.029 mm-1,the final R=0.0588 and wR=0.1577.The complex exhibits antimicrobial activities(antimicrobial activities against Staphylococcus aureus and Escherichia codi) by agar diffusion measurement.     

Synthesis,Crystal Structure,Theoretical Calculation,and Photophysical Property of a New Cd(Ⅱ) Complex Based on N-heterocyclic Ligand and Isophthalic Acid

A new metal-organic coordination complex[Cd(imp)(m-bdc)]_n (1,ipm=5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol,m-bdc=isophthalic acid) has been synthesized by hydrothermal reaction and characterized by elemental analysis,thermogravimetric (TG) analysis,infrared spectrum (IR) and single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a=15.373(5),b=16.719(5),c=19.406(6)A,β=106.995(5)°,V=4770(2)A³,C₂₈H₁₈Cd N₄O₆,M_r=618.86,D_c=1.724 g/cm³,μ(Mo Kα)=0.971 mm^–1,F(000)=2480,Z=8,the final R=0.0391 and w R=0.1044 for 4701 observed reflections (I>2σ(I)).Single-crystal X-ray diffraction reveals that 1 exhibits a one-dimensional (1D) double-chain architecture,and the H-bond intersections link the 1D double-chain architecture into a 2D layer structure.TG analysis shows clear courses of weight loss,which corresponds to the decomposition of different ligands.We also study the luminescent properties of complex 1.In addition,to elucidate the essential electronic characters of this complex,theoretical calculation analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program.     

Synthesis and Crystal Structure of Bis{2-bromo- 4-chloro-6-[(2-isopropylammonioethylimino)-methyl]phenolato}bisthiocyanatozinc(Ⅱ)

A Schiff base zinc(Ⅱ) complex [Zn(C12H16BrClN2O)2(NCS)2] was prepared and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P with a = 8.414(1), b = 9.124(1), c = 22.212(3) (A), α = 79.177(2), β = 86.296(2), γ = 89.899(2)o, V = 1671.3(4) (A)3, Z = 2, Dc = 1.631 g/cm3, Mr = 820.79, λ(MoKα) = 0.71073 (A), μ = 3.444 mm-1, F(000) = 824, R = 0.0646 and wR = 0.1179. A total of 7371 unique reflections were collected, of which 3904 with I＞2σ(I) were observed. The complex crystallizes with two half-molecules per asymmetric unit and each mononuclear molecule is centrosymmetric. The Zn atom lying at the inversion centre is six-coordinated in a slightly distorted octahedral geometry by two phenolate O atoms and two imine N atoms from two Schiff base ligands, as well as two N atoms from two thiocyanate anions. In the crystal structure, the combination of π-π stacking interactions and intermolecular hydrogen bonds (N-H…Br, N-H…O, N-H…N, C-H…O, C-H…S and C-H…Cl) leads to a three-dimensional network.     

Synthesis,Crystal Structure and Magnetic Properties of a Ni（Ⅱ） Supramolecular Complex Based on Aromatic Polycarboxylate Ligand

A Ni(Ⅱ) supramolecular complex,[Ni 2 (btec)(3py) 2 (H 2 O) 8 ](H 2 O) 4 (1),has been synthesized by Ni(ClO 4) 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid (H 4 btec) and terminal ligand 3-hydroxypyridine (3py) in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637(12),b=9.4138(13),c=10.3611(14),α=67.9540(10),β=85.1740(10),γ=76.9890(10)°,V=754.33(18) 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F(000)=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I > 2σ(Ⅰ).The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.     

Synthesis,Structure and Characterization of a Cd(Ⅱ) Polymer Based on 6-Hydroxynicotinic Acid

A new 2D layered Cd(II) coordination polymer,[Cd(HnicO)(phen)(NO3)]n 1(H2nicO = 6-hydroxynicotinic acid,phen = 1,10-phenanthroline),has been hydrothermally synthesized and characterized by elemental analysis,IR,and single-crystal X-ray diffraction.It crystallizes in the monoclinic system,space group P21/c with a = 11.1107(2),b = 13.7639(2),c = 12.1457(4) ,β = 108.695(1)°,V = 1759.40(7) 3,Z = 4,Mr = 492.72,F(000) = 976,Dc = 1.860 g/cm3,μ = 1.289 mm-1,the final R = 0.0205 and wR = 0.0550 for 3663 observed reflections(I > 2σ(I)).X-ray single-crystal structural analyses reveal that in complex 1,the H2nicO ligands and Cd(II) nodes define the structure to be(4,4) 2D nets which are further assembled into the final 3D architecture via supramolecular interactions such as hydrogen bonds and aromatic interactions.Moreover,the solid-state luminescent study shows the title polymer possesses intense luminescent property at room temperature.