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 ioniza...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） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, 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.展开更多
A new acetate radical bridged dinuclear copper（ Ⅱ ） complex [（C8H9NO2）2- Cu2（CH3COO）4] has been synthesized by the reaction of Cu（OAc）2 with pyridine-3-ethyl formate and further characterized by X-ray single-...A new acetate radical bridged dinuclear copper（ Ⅱ ） complex [（C8H9NO2）2- Cu2（CH3COO）4] has been synthesized by the reaction of Cu（OAc）2 with pyridine-3-ethyl formate and further characterized by X-ray single-crystal diffraction. Crystal data for the title compound： triclinic system, space group Pí, with a = 8.1654（14）, b = 9.7010（16）, c = 9.9005（17） A, α = 83.266（2）, β = 78.887（2）, γ = 72.881（2）°, V= 733.9（2） A^3, Mr = 665.58, Z = 1, Dc = 1.506 g/cm^3, F（000） = 342,μ = 1.510 mm^-1, the final R = 0.0392 and wR = 0.1005. According to the structural determination, each unit of the title compound is composed of two Cu（ Ⅱ ） atoms, two pyridine-3-ethyl formate molecules and four acetate ions. Each Cu（Ⅱ） coordinates to oxygen atoms of acetate and nitrogen atoms of pyridine- 3-ethyl formate ligand to give a six-coordinate distorted octahedral geometry. It is worth mentioning that strong Cu-Cu bond can be observed in the title compound.展开更多
A novel Zn（Ⅱ） complex, [ZnL2（H2O）4]·H2O（1, HL = 2-（nicotinoyloxy）acetic acid）, was synthesized using Zn（OAc）2·2H2O and 2-（nicotinoyloxy）acetic acid as raw materials. Its structure has been eluci...A novel Zn（Ⅱ） complex, [ZnL2（H2O）4]·H2O（1, HL = 2-（nicotinoyloxy）acetic acid）, was synthesized using Zn（OAc）2·2H2O 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.展开更多
A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diff...A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.展开更多
Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid w...Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid with HgBr2 and CuCl2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly,（5-chloro-quinolin-8-yloxy）acetic acid is changed as 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L） in complexes 1 and 2. Crystal data for 1： C12H10Br2 Cl Hg NO3, Mr = 612.07, triclinic, space group P1 with a = 8.5983（7）, b = 9.7726（6）, c = 10.1549（6） A, α = 66.355（6）, β = 77.067（8）, γ = 78.803（8）°, V = 756.6（9）A^3, Z = 2, Dc = 2.687 g/cm^3, F（000） = 560, μ = 15.633 mm^-1, R = 0.0351 and w R = 0.0504. Crystal data for 2： C24H20Cl4 Cu N2O6, Mr = 637.76, triclinic, space group P1 with a = 10.5324（9）, b = 11.2377（16）, c = 12.0143（12） ？, α = 83.413（11）, β = 64.475（9）, γ = 83.144（11）°, V = 1270.9（2） ？3, Z = 2, Dc = 1.667 g/cm3, F（000） = 646, μ = 1.324 mm-1, R = 0.0408 and wR = 0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C–H…π stacking interactions and intermolecular C–H…Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C–H…Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.展开更多
基金supported by the National Basic Research Program of China(No.2014CB643401)the National Natural Science Foundation of China(Nos.51134007 and 51474256)
文摘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） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, 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.
文摘A new acetate radical bridged dinuclear copper（ Ⅱ ） complex [（C8H9NO2）2- Cu2（CH3COO）4] has been synthesized by the reaction of Cu（OAc）2 with pyridine-3-ethyl formate and further characterized by X-ray single-crystal diffraction. Crystal data for the title compound： triclinic system, space group Pí, with a = 8.1654（14）, b = 9.7010（16）, c = 9.9005（17） A, α = 83.266（2）, β = 78.887（2）, γ = 72.881（2）°, V= 733.9（2） A^3, Mr = 665.58, Z = 1, Dc = 1.506 g/cm^3, F（000） = 342,μ = 1.510 mm^-1, the final R = 0.0392 and wR = 0.1005. According to the structural determination, each unit of the title compound is composed of two Cu（ Ⅱ ） atoms, two pyridine-3-ethyl formate molecules and four acetate ions. Each Cu（Ⅱ） coordinates to oxygen atoms of acetate and nitrogen atoms of pyridine- 3-ethyl formate ligand to give a six-coordinate distorted octahedral geometry. It is worth mentioning that strong Cu-Cu bond can be observed in the title compound.
基金supported by the National Natural Science Foundation of China(No.21171132)the Project of Shandong Province Higher Educational Science and Technology Program(J14LC01)Science Foundation of Weifang
文摘A novel Zn（Ⅱ） complex, [ZnL2（H2O）4]·H2O（1, HL = 2-（nicotinoyloxy）acetic acid）, was synthesized using Zn（OAc）2·2H2O 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.
基金supported by Guangxi Provincial Department of Education(No.KY2015ZD130)the Natural Science Foundation of Guangxi Province(No.2013GXNSFBA019030)the financial support from the Natural Science Foundation of Qinzhou University(No.2014PY-GJ05)
文摘A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.
基金Supported by Key Laboratory of Organic Synthesis of Jiangsu Province(KJS1308)
文摘Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid with HgBr2 and CuCl2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly,（5-chloro-quinolin-8-yloxy）acetic acid is changed as 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L） in complexes 1 and 2. Crystal data for 1： C12H10Br2 Cl Hg NO3, Mr = 612.07, triclinic, space group P1 with a = 8.5983（7）, b = 9.7726（6）, c = 10.1549（6） A, α = 66.355（6）, β = 77.067（8）, γ = 78.803（8）°, V = 756.6（9）A^3, Z = 2, Dc = 2.687 g/cm^3, F（000） = 560, μ = 15.633 mm^-1, R = 0.0351 and w R = 0.0504. Crystal data for 2： C24H20Cl4 Cu N2O6, Mr = 637.76, triclinic, space group P1 with a = 10.5324（9）, b = 11.2377（16）, c = 12.0143（12） ？, α = 83.413（11）, β = 64.475（9）, γ = 83.144（11）°, V = 1270.9（2） ？3, Z = 2, Dc = 1.667 g/cm3, F（000） = 646, μ = 1.324 mm-1, R = 0.0408 and wR = 0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C–H…π stacking interactions and intermolecular C–H…Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C–H…Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.
