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2014 Volume 33 Issue 3
2014, 33(3): 325-332
Abstract:
Nickel(Ⅱ) complexes Ni(L1)2 (1) and Ni(L2)2·CH3CN·H2O (2) (L1Cl=2-(3-benzyl-2,3-dihydroimidazlo-1-yl)-N-(pyridin-2-yl)acetamide, chloride salt, L2Cl=2-(3-naphthalene-2-ylmethyl)-2,3-dihydro-imidazlo-1-yl)-N-phenylacetamide, chloride salt) with amide-functionalized imidazolium NHC ligand were synthesized and determined by single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a=9.2561(19), b=15.138(3), c=20.750(4) Å, β=90.216(3)°, V=2907.3(10) Å3 and Z=4. Complex 2 crystallizes in the orthorhombic system, space group Pbca with a=15.5469(16), b=15.3521(15), c=31.177(3) Å, V=7441.2(13) Å3 and Z=8. They are stable in the air and formed via intermolecular weak interactions, including C-H…π contacts and C-H…O hydrogen bonds. Complex 1 was applied in Suzuki coupling reaction through the investigation of reaction conditions under the optimal choice conditions: 80℃, K3PO4, 3% mol catalysts, 6% mol PPh3 and toluene as solvent system could afford 96% yield in 5 h.
Nickel(Ⅱ) complexes Ni(L1)2 (1) and Ni(L2)2·CH3CN·H2O (2) (L1Cl=2-(3-benzyl-2,3-dihydroimidazlo-1-yl)-N-(pyridin-2-yl)acetamide, chloride salt, L2Cl=2-(3-naphthalene-2-ylmethyl)-2,3-dihydro-imidazlo-1-yl)-N-phenylacetamide, chloride salt) with amide-functionalized imidazolium NHC ligand were synthesized and determined by single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a=9.2561(19), b=15.138(3), c=20.750(4) Å, β=90.216(3)°, V=2907.3(10) Å3 and Z=4. Complex 2 crystallizes in the orthorhombic system, space group Pbca with a=15.5469(16), b=15.3521(15), c=31.177(3) Å, V=7441.2(13) Å3 and Z=8. They are stable in the air and formed via intermolecular weak interactions, including C-H…π contacts and C-H…O hydrogen bonds. Complex 1 was applied in Suzuki coupling reaction through the investigation of reaction conditions under the optimal choice conditions: 80℃, K3PO4, 3% mol catalysts, 6% mol PPh3 and toluene as solvent system could afford 96% yield in 5 h.
2014, 33(3): 333-338
Abstract:
One novel organically templated zincophophate (C5N2H14)·[Zn3(OH2)(PO4)2(HPO4)] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/n, with a=9.7904(11), b=14.0287(14), c=11.8651(13) Å, β=104.690(3)°, V=1576.4(3) Å3, Z=4, T=296(2) K, Mr=601.31 and Dc=2.533 g/cm3. The compound consists of a macroanionic [Zn3(OH2)(PO4)2(HPO4)]2- framework and (C5N2H14)2+ cations, and its structure is built up from ZnO3(OH2), ZnO4, HPO4 and PO4 tetrahedral units that result in 4, 8 and 10-ring channels.
One novel organically templated zincophophate (C5N2H14)·[Zn3(OH2)(PO4)2(HPO4)] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/n, with a=9.7904(11), b=14.0287(14), c=11.8651(13) Å, β=104.690(3)°, V=1576.4(3) Å3, Z=4, T=296(2) K, Mr=601.31 and Dc=2.533 g/cm3. The compound consists of a macroanionic [Zn3(OH2)(PO4)2(HPO4)]2- framework and (C5N2H14)2+ cations, and its structure is built up from ZnO3(OH2), ZnO4, HPO4 and PO4 tetrahedral units that result in 4, 8 and 10-ring channels.
2014, 33(3): 339-344
Abstract:
A new two-dimensional (2D) barium(Ⅱ) coordination polymer [Ba(3-NPA)]n (1) has been obtained by the hydro/solvothermal reaction of the corresponding metal salt with 3-nitrophthalic acid (3-NPAH2). Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. Compound 1 crystallizes in triclinic, space group P1 with a=4.9611(3), b=7.2599(4), c=12.9463(8) Å, α=89.0892(2), β=80.546(2), γ=73.211(2)°, V=440.1(5) Å3, Z=2, C8H3BaNO6, Mr=346.45, Dc=2.614 g·cm-3, μ=4.526 mm-1, S=1.035, F(000)=324, R=0.0168 and wR=0.0471 for 1712 observed reflections with I>2σ(I). (Δρ)max=0.458, (Δρ)min=-0.565 e·Å-3 and (Δ/σ)max=0.001. In compound 1, each 3-NPA2- ligand links six Ba(Ⅱ) ions and each Ba(Ⅱ) ion attaches to six 3-NPA2- ligands to form an inorganic layer structure in the ab-plane. The phenyl groups of 3-NPA2-ligands are grafted on the two sides of the inorganic layer, resulting in a two-dimensional (2D) layered structure. Furthermore, the thermal stability and luminescent properties of compound 1 have also been investigated in detail.
A new two-dimensional (2D) barium(Ⅱ) coordination polymer [Ba(3-NPA)]n (1) has been obtained by the hydro/solvothermal reaction of the corresponding metal salt with 3-nitrophthalic acid (3-NPAH2). Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. Compound 1 crystallizes in triclinic, space group P1 with a=4.9611(3), b=7.2599(4), c=12.9463(8) Å, α=89.0892(2), β=80.546(2), γ=73.211(2)°, V=440.1(5) Å3, Z=2, C8H3BaNO6, Mr=346.45, Dc=2.614 g·cm-3, μ=4.526 mm-1, S=1.035, F(000)=324, R=0.0168 and wR=0.0471 for 1712 observed reflections with I>2σ(I). (Δρ)max=0.458, (Δρ)min=-0.565 e·Å-3 and (Δ/σ)max=0.001. In compound 1, each 3-NPA2- ligand links six Ba(Ⅱ) ions and each Ba(Ⅱ) ion attaches to six 3-NPA2- ligands to form an inorganic layer structure in the ab-plane. The phenyl groups of 3-NPA2-ligands are grafted on the two sides of the inorganic layer, resulting in a two-dimensional (2D) layered structure. Furthermore, the thermal stability and luminescent properties of compound 1 have also been investigated in detail.
2014, 33(3): 345-352
Abstract:
A novel 2-D {[Cd4(tpt)2(Cl)4(2,4-pdc)2]·4H2O}n (1) has been synthesized from the hydrothermal reaction of 3,5,6-tris(2-pyridyl)-1,3,5-triazine (tpt), hydrated CdCl2, and 2,4-dicarboxylic acid (2,4-H2pdc). Compound 1 crystallizes in triclinic, P1 space group with α=8.9434(5), b=9.5486(7), c=17.5772 (8) Å, a=75.014 (5), β=83.778(5), γ=68.304(6)°, V=1347.14(14) Å3, C50H38Cd4Cl4N14O12, Mr=1618.32, Dc=1.990 g/cm3, S=0.95, μ(MoKα)=1.83 mm-1, F(000)=788, Z=1, R=0.039 and wR=0.080. The structure consists of tetranuclear [Cd4(tpt)2(Cl)4]4+ cores as the secondary building unit, which is further connected by the ligand pdc2- to give a 2-D extended structure. Tpt entities are located on both sides of each 2-D framework and act as ‘side arms' to form a corrugated layer and the adjacent layers are arranged in a tongue-and-groove interdigitating fashion. 1 was characterized by IR, TGA, PX1RD, and elemental analysis. The solid state luminescent properties were also investigated at room temperature.
A novel 2-D {[Cd4(tpt)2(Cl)4(2,4-pdc)2]·4H2O}n (1) has been synthesized from the hydrothermal reaction of 3,5,6-tris(2-pyridyl)-1,3,5-triazine (tpt), hydrated CdCl2, and 2,4-dicarboxylic acid (2,4-H2pdc). Compound 1 crystallizes in triclinic, P1 space group with α=8.9434(5), b=9.5486(7), c=17.5772 (8) Å, a=75.014 (5), β=83.778(5), γ=68.304(6)°, V=1347.14(14) Å3, C50H38Cd4Cl4N14O12, Mr=1618.32, Dc=1.990 g/cm3, S=0.95, μ(MoKα)=1.83 mm-1, F(000)=788, Z=1, R=0.039 and wR=0.080. The structure consists of tetranuclear [Cd4(tpt)2(Cl)4]4+ cores as the secondary building unit, which is further connected by the ligand pdc2- to give a 2-D extended structure. Tpt entities are located on both sides of each 2-D framework and act as ‘side arms' to form a corrugated layer and the adjacent layers are arranged in a tongue-and-groove interdigitating fashion. 1 was characterized by IR, TGA, PX1RD, and elemental analysis. The solid state luminescent properties were also investigated at room temperature.
2014, 33(3): 353-360
Abstract:
To improve the electrical conductivity of LiFePO4 cathode materials, the ZnO modified LiFePO4/C cathode materials are synthesized by a two-step process including solid state synthesis method and precipitation method. The structures and compositions of ZnO modified LiFePO4/C cathode materials are characterized and analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy, which indicates that the existence of ZnO has little or no effect on the crystal structure, particles size and morphology of LiFePO4. The electrochemical performances are also characterized and analyzed with charge-discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the existence of ZnO improves the specific capability and lithium ion diffusion rate of LiFePO4 cathode materials and reduces the charge transfer resistance of cell, and the one with 3 wt% ZnO exhibits the best electrochemical performance.
To improve the electrical conductivity of LiFePO4 cathode materials, the ZnO modified LiFePO4/C cathode materials are synthesized by a two-step process including solid state synthesis method and precipitation method. The structures and compositions of ZnO modified LiFePO4/C cathode materials are characterized and analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy, which indicates that the existence of ZnO has little or no effect on the crystal structure, particles size and morphology of LiFePO4. The electrochemical performances are also characterized and analyzed with charge-discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the existence of ZnO improves the specific capability and lithium ion diffusion rate of LiFePO4 cathode materials and reduces the charge transfer resistance of cell, and the one with 3 wt% ZnO exhibits the best electrochemical performance.
2014, 33(3): 361-366
Abstract:
A new Gd coordination polymer based on 2-(pyridin-3-yl)-1H-imidazole-4,5-dicar-boxylate, formulated as {[Gd2(HPyIDC)2(H2O)5]·(bpy)·(NO3)2·3H2O}n (1, bpy=4,4'-bipyridine) has been synthesized under hydrothermal conditions. The compound crystallizes in triclinic, space group P1 with a=11.451(2), b=11.596(2), c=15.7333(3) Å, β=79.47(3)°, Z=2, V=1948.6(7) Å3, C30H34Gd2N10O22, Dc=2.047 g/cm3, Mr=1201.17, λ(MoKa)=0.71073 Å, μ=3.477 mm-1, F(000)=1176, the final R=0.0554 and wR=0.1181. Polymer 1 is a 2D network built up from 4-connected HPyIDC2- anion and 4-connected Gd ions. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.
A new Gd coordination polymer based on 2-(pyridin-3-yl)-1H-imidazole-4,5-dicar-boxylate, formulated as {[Gd2(HPyIDC)2(H2O)5]·(bpy)·(NO3)2·3H2O}n (1, bpy=4,4'-bipyridine) has been synthesized under hydrothermal conditions. The compound crystallizes in triclinic, space group P1 with a=11.451(2), b=11.596(2), c=15.7333(3) Å, β=79.47(3)°, Z=2, V=1948.6(7) Å3, C30H34Gd2N10O22, Dc=2.047 g/cm3, Mr=1201.17, λ(MoKa)=0.71073 Å, μ=3.477 mm-1, F(000)=1176, the final R=0.0554 and wR=0.1181. Polymer 1 is a 2D network built up from 4-connected HPyIDC2- anion and 4-connected Gd ions. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.
2014, 33(3): 367-386
Abstract:
Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.
Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.
2014, 33(3): 387-394
Abstract:
A new 2D barium-organic framework, [Ba2(Hbidc)2]n (1, Hbidc=1H-benzimida-zole-5, 6-dicarboxylate), has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, TGA, powder X-ray diffraction, and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a=6.8785(14), b=9.4558(19), c=14.641(3) Å, α=86.22(3), β=82.27(3), γ=88.40(3)°, V=941.4(3) Å3, Z=2, Mr=682.96, Dc=2.409 g/cm3, μ(MoKα)=4.217 mm-1, F(000)=640, the final R=0.0587 and wR=0.1619 for 3030 observed reflections with I>2σ(I). Structural determination reveals that 1 exhibits an interesting 2D layer structure constructed by carboxylate groups of Hbidc ligands and shows good thermal stability (up to 400℃). Solid-state 1 emits intense indigotin photoluminescence with fluorescence lifetime of 62.13 (408 nm) at room temperature. The H3bidc ligand and its barium complex have been screened for antibacterial activity against several bacteria strains, and the results are compared with the activity of penicillin.
A new 2D barium-organic framework, [Ba2(Hbidc)2]n (1, Hbidc=1H-benzimida-zole-5, 6-dicarboxylate), has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, TGA, powder X-ray diffraction, and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a=6.8785(14), b=9.4558(19), c=14.641(3) Å, α=86.22(3), β=82.27(3), γ=88.40(3)°, V=941.4(3) Å3, Z=2, Mr=682.96, Dc=2.409 g/cm3, μ(MoKα)=4.217 mm-1, F(000)=640, the final R=0.0587 and wR=0.1619 for 3030 observed reflections with I>2σ(I). Structural determination reveals that 1 exhibits an interesting 2D layer structure constructed by carboxylate groups of Hbidc ligands and shows good thermal stability (up to 400℃). Solid-state 1 emits intense indigotin photoluminescence with fluorescence lifetime of 62.13 (408 nm) at room temperature. The H3bidc ligand and its barium complex have been screened for antibacterial activity against several bacteria strains, and the results are compared with the activity of penicillin.
2014, 33(3): 395-400
Abstract:
Ethyl 3,9-dimethyl-7-phenyl-6H-dibenzo[b,d]pyran-6-one-8-carboxylate (C24H20O4, Mr=372.40) has been synthesized and its structure was determined by 1H and 13C NMR, ESI-MS, elemental analysis, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/n, with a=8.3674(11), b=10.6683(14), c=11.3817(15) Å, α=95.596(2), β=109.866(2), γ=94.495(2)°, V=944.2(2) Å3, Z=2, Dc=1.310 g/cm3, μ=0.089 mm-1, F(000)=392, R=0.0482 and wR=0.1281 for 2916 observed reflections with I>2σ(I). In the crystal structure, the fused tricyclic nucleus of the title compound is not fully coplanar. Analysis of the crystal packing indicates aromatic π-π stacking interactions occurring between the fused tricyclic aromatic rings of neighboring molecules in which a maximum overlap of the π-electron systems was achieved. Fluorescence and thermal studies indicate that compound 3 has good optical properties and thermal stability.
Ethyl 3,9-dimethyl-7-phenyl-6H-dibenzo[b,d]pyran-6-one-8-carboxylate (C24H20O4, Mr=372.40) has been synthesized and its structure was determined by 1H and 13C NMR, ESI-MS, elemental analysis, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/n, with a=8.3674(11), b=10.6683(14), c=11.3817(15) Å, α=95.596(2), β=109.866(2), γ=94.495(2)°, V=944.2(2) Å3, Z=2, Dc=1.310 g/cm3, μ=0.089 mm-1, F(000)=392, R=0.0482 and wR=0.1281 for 2916 observed reflections with I>2σ(I). In the crystal structure, the fused tricyclic nucleus of the title compound is not fully coplanar. Analysis of the crystal packing indicates aromatic π-π stacking interactions occurring between the fused tricyclic aromatic rings of neighboring molecules in which a maximum overlap of the π-electron systems was achieved. Fluorescence and thermal studies indicate that compound 3 has good optical properties and thermal stability.
2014, 33(3): 401-406
Abstract:
Proton-conductive crystalline metal-organic framework nickel(Ⅱ) benzenetricar-boxylate Ni3(BTC)2·12H2O(MOF-Ni) was prepared by the reaction of nickel(Ⅱ) nitrate and 1,3,5-benzenetricarboxylic (BTC) acid in a mixed solvent of N,N-dimethylformami-de(DMF)/C2H5OH/H2O (1:1:1, ν/ν) at low temperature and short reaction time. It was characterized by thermogravimetric analyses (TG), FT-IR and N2 adsorption-desorption. Single-crystal X-ray diffraction analysis indicated that the complex belongs to monoclinic system, space group C2 with a=17.407(6), b=12.878(5), c=6.542(2) Å, β=112.07°, V=1359.0(8) Å3, Dc=1.971 g/cm3, μ=2.166 mm-1 and Z=2. Linear polarization resistance (LPR) analysis showed that the complex possesses semiconducting properties.
Proton-conductive crystalline metal-organic framework nickel(Ⅱ) benzenetricar-boxylate Ni3(BTC)2·12H2O(MOF-Ni) was prepared by the reaction of nickel(Ⅱ) nitrate and 1,3,5-benzenetricarboxylic (BTC) acid in a mixed solvent of N,N-dimethylformami-de(DMF)/C2H5OH/H2O (1:1:1, ν/ν) at low temperature and short reaction time. It was characterized by thermogravimetric analyses (TG), FT-IR and N2 adsorption-desorption. Single-crystal X-ray diffraction analysis indicated that the complex belongs to monoclinic system, space group C2 with a=17.407(6), b=12.878(5), c=6.542(2) Å, β=112.07°, V=1359.0(8) Å3, Dc=1.971 g/cm3, μ=2.166 mm-1 and Z=2. Linear polarization resistance (LPR) analysis showed that the complex possesses semiconducting properties.
2014, 33(3): 407-414
Abstract:
The title compound, N-(2-(1,3,4-oxadiazol-2-yl)phenyl)-2,3-dimethylaniline, was synthesized and studied by single-crystal X-ray diffraction method. The structure of the product was confirmed by IR, 1H-and 13C-NMR spectroscopy, elemental analysis and mass spectrometry. These experimental studies were supported by theoretical optimizations.
The title compound, N-(2-(1,3,4-oxadiazol-2-yl)phenyl)-2,3-dimethylaniline, was synthesized and studied by single-crystal X-ray diffraction method. The structure of the product was confirmed by IR, 1H-and 13C-NMR spectroscopy, elemental analysis and mass spectrometry. These experimental studies were supported by theoretical optimizations.
2014, 33(3): 415-421
Abstract:
In this study, two new co-crystals based on rigid imidazolium ligand (2,2'-((1,1'-biphenyl)-4,4'-diyl)bis(2H-imidazo[1,5-a]pyridine-4-ium) hexafluorophosphate (L)) and 4,4'-bipyridine (Bpy) and benzene (Ben), formulated as L(Bpy)0.5 (co-crystal 1) and L(Ben) (co-crystal 2), were obtained. Crystal data for 1: P1 space group with a=10.921(4), b=16.998(6), c=17.666(6) Å, α=95.720(7), β=104.272(7), γ=93.340(6)°, V=3150.5(19) Å3 and Z=2; and crystal data for 2: monoclinic C2/m space group with a=25.90(2), b=9.631(9), c=6.371(6) Å, β=95.26(2)°, V=1583(2) Å3 and Z=2. Co-crystal 1 was dependent on hydrogen bonds and π…π stacking, while only hydrogen bonds are present in 2. Two new co-crystals were characterized by IR, NMR spectra, thermogravimetric and ultraviolet absorption analyses.
In this study, two new co-crystals based on rigid imidazolium ligand (2,2'-((1,1'-biphenyl)-4,4'-diyl)bis(2H-imidazo[1,5-a]pyridine-4-ium) hexafluorophosphate (L)) and 4,4'-bipyridine (Bpy) and benzene (Ben), formulated as L(Bpy)0.5 (co-crystal 1) and L(Ben) (co-crystal 2), were obtained. Crystal data for 1: P1 space group with a=10.921(4), b=16.998(6), c=17.666(6) Å, α=95.720(7), β=104.272(7), γ=93.340(6)°, V=3150.5(19) Å3 and Z=2; and crystal data for 2: monoclinic C2/m space group with a=25.90(2), b=9.631(9), c=6.371(6) Å, β=95.26(2)°, V=1583(2) Å3 and Z=2. Co-crystal 1 was dependent on hydrogen bonds and π…π stacking, while only hydrogen bonds are present in 2. Two new co-crystals were characterized by IR, NMR spectra, thermogravimetric and ultraviolet absorption analyses.
2014, 33(3): 422-428
Abstract:
UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G* level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.
UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G* level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.
2014, 33(3): 429-433
Abstract:
The title compound has been synthesized by the reaction of 4-tert-butyl-5-(1,2,4-triazol-1-yl)-2-aminothiazole with propionic anhydride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a=18.441(2), b=8.3284(9), c=19.257(2) Å, Z=8, V=2957.5(5) Å3, Mr=279.37, Dc=1.255 mg/m3, S=1.033, μ=0.219 mm-1, F(000)=1184, the final R=0.0349 and wR=0.0876 for 2629 observed reflections (I>2σ(I)). X-ray crystal structure presents the intermolecular N-H…N hydrogen bond, which plays an important role in stabilizing the crystal structure. The preliminary bioassay indicates that the title compound exhibits potent fungicidal activity against R. Solani (25 mg/L) with inhibition rate of 80.0%.
The title compound has been synthesized by the reaction of 4-tert-butyl-5-(1,2,4-triazol-1-yl)-2-aminothiazole with propionic anhydride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a=18.441(2), b=8.3284(9), c=19.257(2) Å, Z=8, V=2957.5(5) Å3, Mr=279.37, Dc=1.255 mg/m3, S=1.033, μ=0.219 mm-1, F(000)=1184, the final R=0.0349 and wR=0.0876 for 2629 observed reflections (I>2σ(I)). X-ray crystal structure presents the intermolecular N-H…N hydrogen bond, which plays an important role in stabilizing the crystal structure. The preliminary bioassay indicates that the title compound exhibits potent fungicidal activity against R. Solani (25 mg/L) with inhibition rate of 80.0%.
2014, 33(3): 434-440
Abstract:
Two coordination polymers, namely {[Ni(cpna)(H2biim)(H2O)]·H2O}n (1) and {[Mn(cpna)(H2biim)]·H2O}n (2) (H2cpna=5-(2'-carboxylphenyl) nicotic acid, H2biim=2,2'-biimidazole) have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) step-like chain structure, which further builds a three-dimensional (3D) supra-molecular architecture via O-H…O and N-H…O hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional (1D) double chain structure, which is further assembled into a 3D supramolecular framework by N-H…O hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni(Ⅱ) centers, with g=2.11 and J=-1.87 cm-1.
Two coordination polymers, namely {[Ni(cpna)(H2biim)(H2O)]·H2O}n (1) and {[Mn(cpna)(H2biim)]·H2O}n (2) (H2cpna=5-(2'-carboxylphenyl) nicotic acid, H2biim=2,2'-biimidazole) have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) step-like chain structure, which further builds a three-dimensional (3D) supra-molecular architecture via O-H…O and N-H…O hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional (1D) double chain structure, which is further assembled into a 3D supramolecular framework by N-H…O hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni(Ⅱ) centers, with g=2.11 and J=-1.87 cm-1.
2014, 33(3): 441-447
Abstract:
Two new 1,3-oxazin derivatives, C22H24N2O5 (3I) and C19H16N2O5 (3Ⅱ), have been synthesized via an unusual cascade reaction. The attractive aspect of this cascade reaction is that the novel construction of 1,3-oxazine and the direct C-N bond formation from C-C bond can be easily achieved via pyridine-mediated acylation in a one-pot operation. Both compounds have been synthesized and characterized by elemental analysis, IR, NMR spectra and X-ray single-crystal diffraction. Compound 3I crystallizes in monoclinic, space group P21/n with a=16.282(4), b=7.4117(18), c=17.256(5) Å, β=103.193(9)°, V=2027.4(9) Å3, Mr=396.43, Z=4, Dc=1.299 g/cm3, F(000)=840, MoKa radiation (λ=0.71073 Å), the final R=0.0771 and wR=0.1582 for 3662 were observed reflections with I>2σ(I). Compound 3Ⅱ crystallizes in triclinic, space group P1 with a=7.1265(9), b=10.1071(13), c=23.529(3) Å, α=97.463(9), β=96.981(9), γ=94.345(9)°, V=1600.5(4) Å3, Z=4, Dc=1.409 g/cm3, F(000)=736, CuKa radiation (λ=1.54186 Å), the final R=0.0515 and wR=0.1241 for 4920 observed reflections with I>2σ(I). The preliminary antibacterial activities of 2 and 3 against E. coli and S. aureus were investigated. The results showed that the inhibiting effect of 3 was higher than that of 2.
Two new 1,3-oxazin derivatives, C22H24N2O5 (3I) and C19H16N2O5 (3Ⅱ), have been synthesized via an unusual cascade reaction. The attractive aspect of this cascade reaction is that the novel construction of 1,3-oxazine and the direct C-N bond formation from C-C bond can be easily achieved via pyridine-mediated acylation in a one-pot operation. Both compounds have been synthesized and characterized by elemental analysis, IR, NMR spectra and X-ray single-crystal diffraction. Compound 3I crystallizes in monoclinic, space group P21/n with a=16.282(4), b=7.4117(18), c=17.256(5) Å, β=103.193(9)°, V=2027.4(9) Å3, Mr=396.43, Z=4, Dc=1.299 g/cm3, F(000)=840, MoKa radiation (λ=0.71073 Å), the final R=0.0771 and wR=0.1582 for 3662 were observed reflections with I>2σ(I). Compound 3Ⅱ crystallizes in triclinic, space group P1 with a=7.1265(9), b=10.1071(13), c=23.529(3) Å, α=97.463(9), β=96.981(9), γ=94.345(9)°, V=1600.5(4) Å3, Z=4, Dc=1.409 g/cm3, F(000)=736, CuKa radiation (λ=1.54186 Å), the final R=0.0515 and wR=0.1241 for 4920 observed reflections with I>2σ(I). The preliminary antibacterial activities of 2 and 3 against E. coli and S. aureus were investigated. The results showed that the inhibiting effect of 3 was higher than that of 2.
2014, 33(3): 448-458
Abstract:
In this research, the hydrogen bonds Y…H-X (X=C, N; Y=N, O) of thymine and uracil have been theoretically studied. The results show that hydrogen bond leads to bond length elongation and stretches the frequency red-shift of N-H…Y. Meanwhile, the C-H…O bonds shorten and stretch the frequency blue-shift. They all belong to traditional hydrogen bonds. The intermolecular charge transfer caused by the intermolecular hyperconjugation σ*(N-H) → n(Y) and intramolecular charge redistribution by intramolecular hyperconjugation σ(C-H) →σ*(C-N) play important roles in the formation of hydrogen bonds. According to the judgment standards proposed by Bader and Popelier, these hydrogen bonds have typical electron density topological properties. Electrostatic surface potential (ESP) is a useful physicochemical property of a molecule that provides insights into inter-and intramolecular associations, as well as the prediction of likely sites of electrophilic and nucleophilic metabolic attack.
In this research, the hydrogen bonds Y…H-X (X=C, N; Y=N, O) of thymine and uracil have been theoretically studied. The results show that hydrogen bond leads to bond length elongation and stretches the frequency red-shift of N-H…Y. Meanwhile, the C-H…O bonds shorten and stretch the frequency blue-shift. They all belong to traditional hydrogen bonds. The intermolecular charge transfer caused by the intermolecular hyperconjugation σ*(N-H) → n(Y) and intramolecular charge redistribution by intramolecular hyperconjugation σ(C-H) →σ*(C-N) play important roles in the formation of hydrogen bonds. According to the judgment standards proposed by Bader and Popelier, these hydrogen bonds have typical electron density topological properties. Electrostatic surface potential (ESP) is a useful physicochemical property of a molecule that provides insights into inter-and intramolecular associations, as well as the prediction of likely sites of electrophilic and nucleophilic metabolic attack.
2014, 33(3): 459-467
Abstract:
The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid (HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA-, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π…π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction (zJ'=0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.
The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid (HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA-, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π…π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction (zJ'=0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.
2014, 33(3): 468-472
Abstract:
A new Cd(Ⅱ) coordination polymer, namely, [Cd3(1,2,3-BTC)2(L)2]·2.25H2O (1, L=2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,2,3-BTC=1,2,3-ben-zenetricarboxylate), has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=11.650(2), b=12.240(2), c=19.760(4) Å, α=72.01(3), β=77.11(3), γ=83.48(3)°, V=2609.4(9) Å3, Z=2, C56H31Cd3Cl2F2N8O14.25, Mr=1489.99, Dc=1.896 g/cm3, F(000)=1466, μ(MoKa)=1.401 mm-1, R=0.0401 and wR=0.1104. Compound 1 shows a 1D chain structure, and the nei-ghboring 1D chains of 1 are joined together by π…π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.
A new Cd(Ⅱ) coordination polymer, namely, [Cd3(1,2,3-BTC)2(L)2]·2.25H2O (1, L=2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,2,3-BTC=1,2,3-ben-zenetricarboxylate), has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=11.650(2), b=12.240(2), c=19.760(4) Å, α=72.01(3), β=77.11(3), γ=83.48(3)°, V=2609.4(9) Å3, Z=2, C56H31Cd3Cl2F2N8O14.25, Mr=1489.99, Dc=1.896 g/cm3, F(000)=1466, μ(MoKa)=1.401 mm-1, R=0.0401 and wR=0.1104. Compound 1 shows a 1D chain structure, and the nei-ghboring 1D chains of 1 are joined together by π…π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.
2014, 33(3): 473-479
Abstract:
A dinuclear copper complex [Cu2LCl2](ClO4)2 (L=2,2'-(piperazine-1,4-diyl)bis-(N,N-bis(pyridine-2-ylmethyl)ethan-1-amine)) has been synthesized and structurally characterized. It crystallizes in triclinic, space group P1 with a=8.5707(9), b=10.5083(12), c=11.4878(13) Å, α=76.197(2), β=88.271(2), γ=87.855(2)°, V=1003.81(19) Å3, Z=1, F(000)=478, Dc=1.544 Mg/m3, Mr=933.60, μ=1.383 mm-1, the final R=0.0669 and wR=0.1486 for 3675 observed reflections with I>2σ(I). Its catechol oxidase mimic activity was studied spectroscopically by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. The results showed that the kinetics of catechol catalyzed by the complex accorded with the Michaelis-Mentent equation, and the catechol oxidase catalytic activity of the complex increased with increasing the pH values.
A dinuclear copper complex [Cu2LCl2](ClO4)2 (L=2,2'-(piperazine-1,4-diyl)bis-(N,N-bis(pyridine-2-ylmethyl)ethan-1-amine)) has been synthesized and structurally characterized. It crystallizes in triclinic, space group P1 with a=8.5707(9), b=10.5083(12), c=11.4878(13) Å, α=76.197(2), β=88.271(2), γ=87.855(2)°, V=1003.81(19) Å3, Z=1, F(000)=478, Dc=1.544 Mg/m3, Mr=933.60, μ=1.383 mm-1, the final R=0.0669 and wR=0.1486 for 3675 observed reflections with I>2σ(I). Its catechol oxidase mimic activity was studied spectroscopically by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. The results showed that the kinetics of catechol catalyzed by the complex accorded with the Michaelis-Mentent equation, and the catechol oxidase catalytic activity of the complex increased with increasing the pH values.
2014, 33(3): 480-489
Abstract:
Based on the knot theory and researching of network structures of glucomannan molecules, the polysaccharides were analyzed. The link prediction analysis is to further reveal the interactions between polysaccharides, to elaborate QSAR of polysaccharides, and to analyze the network conformation relationships among polysaccharides. We made a classification for glucomannan molecules based on the related domestic and international theories, and investigated their network structures and application prospects. The knot theory and the link predictions not only simplify the glucomannan microscopic descriptions but also play a guiding role in predicting and regulating the structures.
Based on the knot theory and researching of network structures of glucomannan molecules, the polysaccharides were analyzed. The link prediction analysis is to further reveal the interactions between polysaccharides, to elaborate QSAR of polysaccharides, and to analyze the network conformation relationships among polysaccharides. We made a classification for glucomannan molecules based on the related domestic and international theories, and investigated their network structures and application prospects. The knot theory and the link predictions not only simplify the glucomannan microscopic descriptions but also play a guiding role in predicting and regulating the structures.
2014, 33(3): 490-497
Abstract:
Titanium-doped ordered mesoporous alumina with specific structural properties has been prepared by the evaporation induced self-assembly sol-gel method. The results show that the doped titanium helps to stabilize the ordered mesoporous alumina material without influencing the ordered mesoporosity. The textural properties of the obtained sample are related to the amount of doped titanium. When the molar ratio of aluminum to titanium (n(Al)/n(Ti)) is controlled as 10.2, the titanium-doped ordered mesoporous alumina exhibits high surface area (up to 218 m2 g-1), large pore volume (0.42 cm3 g-1) and narrow pore diameter (6.1 nm) after treating at 900℃, showing high thermal stability. Moreover, the obtained sample calcined at 900℃ still maintains ordered mesoporous structure and exhibits high thermal stability.
Titanium-doped ordered mesoporous alumina with specific structural properties has been prepared by the evaporation induced self-assembly sol-gel method. The results show that the doped titanium helps to stabilize the ordered mesoporous alumina material without influencing the ordered mesoporosity. The textural properties of the obtained sample are related to the amount of doped titanium. When the molar ratio of aluminum to titanium (n(Al)/n(Ti)) is controlled as 10.2, the titanium-doped ordered mesoporous alumina exhibits high surface area (up to 218 m2 g-1), large pore volume (0.42 cm3 g-1) and narrow pore diameter (6.1 nm) after treating at 900℃, showing high thermal stability. Moreover, the obtained sample calcined at 900℃ still maintains ordered mesoporous structure and exhibits high thermal stability.
