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2016 Volume 35 Issue 4
2016, 35(4): 505-513
doi: 10.14102/j.cnki.0254-5861.2011-0977
Abstract:
A new metal-organic coordination polymer[Zn(pzdc)(mbix)]n·nH2O (H2pzdc=pyrazine-2,3-dicarboxylic acid, mbix=1,3-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in monoclinic system, space group P21/n with a=8.5519(6), b=14.8764(10), c=16.4108(11) Å, β=103.4520(10)°, V=2030.5(2) Å3, C20H18N6O5Zn, Mr=487.77, Dc=1.596 g/cm3, F(000)=1000, Z=4, μμ(MoKα)=1.257 mm-1, the final R=0.0260 and wR=0.0706 for 3445 observed reflections (I>2σ(I)). The structure of 1 exhibits a one-dimensional chain-like structure. In addition, natural bond orbital (NBO) analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program. The calculation results show obvious covalent interaction between the coordinated atoms and Zn(Ⅱ) ion.
A new metal-organic coordination polymer[Zn(pzdc)(mbix)]n·nH2O (H2pzdc=pyrazine-2,3-dicarboxylic acid, mbix=1,3-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in monoclinic system, space group P21/n with a=8.5519(6), b=14.8764(10), c=16.4108(11) Å, β=103.4520(10)°, V=2030.5(2) Å3, C20H18N6O5Zn, Mr=487.77, Dc=1.596 g/cm3, F(000)=1000, Z=4, μμ(MoKα)=1.257 mm-1, the final R=0.0260 and wR=0.0706 for 3445 observed reflections (I>2σ(I)). The structure of 1 exhibits a one-dimensional chain-like structure. In addition, natural bond orbital (NBO) analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program. The calculation results show obvious covalent interaction between the coordinated atoms and Zn(Ⅱ) ion.
2016, 35(4): 514-520
doi: 10.14102/j.cnki.0254-5861.2011-0982
Abstract:
The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate (KNF) has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF→B1→TSB1→B2→TSB2→B3→TSB3→B4→KNO2+NO2+NO+CO, and the energy barrier of the rate-limiting step is 216.30 kJ·mol-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.
The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate (KNF) has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF→B1→TSB1→B2→TSB2→B3→TSB3→B4→KNO2+NO2+NO+CO, and the energy barrier of the rate-limiting step is 216.30 kJ·mol-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.
2016, 35(4): 521-528
doi: 10.14102/j.cnki.0254-5861.2011-1024
Abstract:
One new polymer,[Na(NPHSNPAB)(CH3OH)]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by 1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex:C17H17N4NaO9S, Mr=476.39, triclinic system, space group P1, a=8.8741(18), b=10.942(2), c=12.039(2) Å, α=65.74(3), β=77.49(3), γ=84.30(3)°, V=1040.3(4) Å3, Z=2, Dc=1.521 g/cm3, λ=0.71073 Å, F(000)=492, S=1.106, R=0.0614 and wR=0.1423 for 2945 observed reflections with I > 2(I). X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C-H…O, N-H…O, O-H…O, and O-H…S hydrogen bonds. Moreover, sodium(I) center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π…π stacking interaction in the polymer. The average bond distance of the two dicyclic units (3.768 Å) indicated strong π…π stacking interaction. The complex displays greenyellow emission at room temperature.
One new polymer,[Na(NPHSNPAB)(CH3OH)]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by 1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex:C17H17N4NaO9S, Mr=476.39, triclinic system, space group P1, a=8.8741(18), b=10.942(2), c=12.039(2) Å, α=65.74(3), β=77.49(3), γ=84.30(3)°, V=1040.3(4) Å3, Z=2, Dc=1.521 g/cm3, λ=0.71073 Å, F(000)=492, S=1.106, R=0.0614 and wR=0.1423 for 2945 observed reflections with I > 2(I). X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C-H…O, N-H…O, O-H…O, and O-H…S hydrogen bonds. Moreover, sodium(I) center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π…π stacking interaction in the polymer. The average bond distance of the two dicyclic units (3.768 Å) indicated strong π…π stacking interaction. The complex displays greenyellow emission at room temperature.
2016, 35(4): 529-536
doi: 10.14102/j.cnki.0254-5861.2011-0896
Abstract:
Two new pleuromutilin derivatives, 14-O-[(4-amino-6-methoxyl-pyrimidine-2-yl)-thioacetyl] mutilin (4) and 14-O-[4-amino-1-methyl-6-oxo-1,6-dihydropyrimidin-2-yl)thioacetyl] mutilin (5), were synthesized and structurally characterized by IR, NMR spectra, HRMS and single-crystal X-ray diffraction. These compounds contain a 5-6-8 tricyclic carbon skeleton and a pyrimidine ring. Compound 4 is in the monoclinic system, space group P1211 with a=10.2517(4), b=12.5655(4), c=10.3435(4) Å, V=1315.69(8) Å3, Z=2, Dc=1.309 g/cm3, F(000)=558, μ=0.166 mm-1, S=1.047, R=0.0457 and wR=0.0934 for 4721 unique reflections (Rint=0.0322) with I > 2σ(I). Compound 5 belongs to the orthorhombic system, space group P212121 with a=7.3667(4), b=13.9990(7), c=29.0434(13) Å, V=2995.1(2) Å3, Z=4, Dc=1.250 g/cm3, F(000)=1216, μ=0.153 mm-1, S=1.031, R=0.0545 and wR=0.0982 for 5242 unique reflections (Rint=0.0476) with I>2σ(I)). The in vitro antibacterial activity study showed the title compounds 4 and 5 displayed slightly less activity against methicillin-resistant Staphylococcus aureus (MRSA) and methicillin-resistant Staphylococcus epidermidis (MRSE), and lower potent against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis) when compared to those of tiamulin fumarate.
Two new pleuromutilin derivatives, 14-O-[(4-amino-6-methoxyl-pyrimidine-2-yl)-thioacetyl] mutilin (4) and 14-O-[4-amino-1-methyl-6-oxo-1,6-dihydropyrimidin-2-yl)thioacetyl] mutilin (5), were synthesized and structurally characterized by IR, NMR spectra, HRMS and single-crystal X-ray diffraction. These compounds contain a 5-6-8 tricyclic carbon skeleton and a pyrimidine ring. Compound 4 is in the monoclinic system, space group P1211 with a=10.2517(4), b=12.5655(4), c=10.3435(4) Å, V=1315.69(8) Å3, Z=2, Dc=1.309 g/cm3, F(000)=558, μ=0.166 mm-1, S=1.047, R=0.0457 and wR=0.0934 for 4721 unique reflections (Rint=0.0322) with I > 2σ(I). Compound 5 belongs to the orthorhombic system, space group P212121 with a=7.3667(4), b=13.9990(7), c=29.0434(13) Å, V=2995.1(2) Å3, Z=4, Dc=1.250 g/cm3, F(000)=1216, μ=0.153 mm-1, S=1.031, R=0.0545 and wR=0.0982 for 5242 unique reflections (Rint=0.0476) with I>2σ(I)). The in vitro antibacterial activity study showed the title compounds 4 and 5 displayed slightly less activity against methicillin-resistant Staphylococcus aureus (MRSA) and methicillin-resistant Staphylococcus epidermidis (MRSE), and lower potent against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis) when compared to those of tiamulin fumarate.
2016, 35(4): 537-544
doi: 10.14102/j.cnki.0254-5861.2011-0883
Abstract:
A typical nitroimine bistriazole (DNABT) was synthesized with high yield (90.4%) by nitration reaction from DABT in HNO3 and NH4NO3. Furthermore, a novel cocrystal (1) consisting of DNABT, H2O and DMSO in a 1:2:2 molar ratio was analysized on the crystal structure. Cocrystal 1 crystallizes in the triclinic system, space group P1 with a=6.3124(18), b=8.233(2), c=9.775(3) Å, β=98.326(4)°, V=481.59(74) Å3, Z=2, Dc=1.55 g/cm3, F(000)=234, μ=0.337 mm-1, S=1.078, the final R=0.0609 and wR=0.2743. Additionally, the crystal structure is built up by four strong and seven weak hydrogen bonds. And the hydrogen bond network contributes to the stability of DNABT molecule. Typical TGA and DSC curves indicate the cocrystal 1 includes one endothermic and one exothermic decomposition processes, and the peak temperature at each process is 164.0 and 245.0℃. The nonisothermal decomposition kinetics analysis was performed by means of the Kissinger and Ozawa methods. The apparent activation energy (Ea) and pre-exponential factor (A) of the two decompositions are 96.0 kJ·mol-1, 108.1 s-1 and 215.8 kJ·mol-1, 1018.9 s-1, respectively.
A typical nitroimine bistriazole (DNABT) was synthesized with high yield (90.4%) by nitration reaction from DABT in HNO3 and NH4NO3. Furthermore, a novel cocrystal (1) consisting of DNABT, H2O and DMSO in a 1:2:2 molar ratio was analysized on the crystal structure. Cocrystal 1 crystallizes in the triclinic system, space group P1 with a=6.3124(18), b=8.233(2), c=9.775(3) Å, β=98.326(4)°, V=481.59(74) Å3, Z=2, Dc=1.55 g/cm3, F(000)=234, μ=0.337 mm-1, S=1.078, the final R=0.0609 and wR=0.2743. Additionally, the crystal structure is built up by four strong and seven weak hydrogen bonds. And the hydrogen bond network contributes to the stability of DNABT molecule. Typical TGA and DSC curves indicate the cocrystal 1 includes one endothermic and one exothermic decomposition processes, and the peak temperature at each process is 164.0 and 245.0℃. The nonisothermal decomposition kinetics analysis was performed by means of the Kissinger and Ozawa methods. The apparent activation energy (Ea) and pre-exponential factor (A) of the two decompositions are 96.0 kJ·mol-1, 108.1 s-1 and 215.8 kJ·mol-1, 1018.9 s-1, respectively.
2016, 35(4): 545-549
doi: 10.14102/j.cnki.0254-5861.2011-0925
Abstract:
The crystal structure of 3-(4-methoxyphenyl)-2-(4-methylbenzoyl)-6,7-dihydro-5H-furo[3,2-g]chromene was obtained by X-ray single-crystal diffraction. The molecule is in the triclinic crystal system, space group P1 with a=11.0745(4), b=13.0953(7), c=15.8773(8) Å, α=92.811(4), β=104.815(4), γ=111.797(4)°, Z=4, the final R=0.0567 and wR=0.1540. X-ray crystal structure data revealed that one asymmetric structure unit of the title compound contained two molecules. The existence of methyl group changed the dihedral angle between furan ring and the phenyl ring at the C2 position of the furo[3,2-g]chromene scaffold as well as the conformation, and had a further influence on the bioactivity of the furo[3,2-g]chromene derivatives.
The crystal structure of 3-(4-methoxyphenyl)-2-(4-methylbenzoyl)-6,7-dihydro-5H-furo[3,2-g]chromene was obtained by X-ray single-crystal diffraction. The molecule is in the triclinic crystal system, space group P1 with a=11.0745(4), b=13.0953(7), c=15.8773(8) Å, α=92.811(4), β=104.815(4), γ=111.797(4)°, Z=4, the final R=0.0567 and wR=0.1540. X-ray crystal structure data revealed that one asymmetric structure unit of the title compound contained two molecules. The existence of methyl group changed the dihedral angle between furan ring and the phenyl ring at the C2 position of the furo[3,2-g]chromene scaffold as well as the conformation, and had a further influence on the bioactivity of the furo[3,2-g]chromene derivatives.
2016, 35(4): 550-558
doi: 10.14102/j.cnki.0254-5861.2011-0874
Abstract:
Solvothermal reaction of manganese(Ⅱ) salt with monosodium 2-sulfoterephthalate (2-NaH2stp) and two multi-pyridine N-containing auxiliary ligands results in the formation of two new complexes formulated with[Mn2(Hstp)2(bpp)2(H2O)4] (1) and[Mn3(stp)2(tpy)3(H2O)](H2O)5 (2) (bpp=benz-2,3-pyrimidine-[2,3-f]-1,10-phenanthroline, tpy=2,2':6',2"-terpyridine). X-ray diffraction structural analyses of two complexes reveal their structural diversity (0D and 1D) due to the difference of auxiliary ligands. 1 is a discrete structure, in which the Mn(Ⅱ) ion is hexa-coordinated with one stp, one bpp ligand and two water molecules. Complex 2 is a one-dimensional (1D) chain-like structure with three crystallographically independent Mn(Ⅱ) ions. The photoluminescent properties could be assigned to the π-π* transition of 2-sulfoterephthalate ligands.
Solvothermal reaction of manganese(Ⅱ) salt with monosodium 2-sulfoterephthalate (2-NaH2stp) and two multi-pyridine N-containing auxiliary ligands results in the formation of two new complexes formulated with[Mn2(Hstp)2(bpp)2(H2O)4] (1) and[Mn3(stp)2(tpy)3(H2O)](H2O)5 (2) (bpp=benz-2,3-pyrimidine-[2,3-f]-1,10-phenanthroline, tpy=2,2':6',2"-terpyridine). X-ray diffraction structural analyses of two complexes reveal their structural diversity (0D and 1D) due to the difference of auxiliary ligands. 1 is a discrete structure, in which the Mn(Ⅱ) ion is hexa-coordinated with one stp, one bpp ligand and two water molecules. Complex 2 is a one-dimensional (1D) chain-like structure with three crystallographically independent Mn(Ⅱ) ions. The photoluminescent properties could be assigned to the π-π* transition of 2-sulfoterephthalate ligands.
2016, 35(4): 559-565
doi: 10.14102/j.cnki.0254-5861.2011-0932
Abstract:
A novel phenoxyimine-based Schiff base ligand and its mononuclear complex[C58H52N2NiO2] (L=2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde) has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, 1H NMR and 13H NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a=14.510(6), b=18.573(7), c=20.961(6) Å, β=123.453(19)°, V=4713(3) Å3, Mr=867.73, Z=4, Dc=1.223 g/cm3, μ=0.456 mm-1, F(000)=1832, the final R=0.0685 and wR=0.1758 (I > 2σ(I)). The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913×107 g of PNB (mol of Ni)-1 h-1, and the yields of these reactions depend on the nature of the substituent in the aromatic ring.
A novel phenoxyimine-based Schiff base ligand and its mononuclear complex[C58H52N2NiO2] (L=2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde) has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, 1H NMR and 13H NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a=14.510(6), b=18.573(7), c=20.961(6) Å, β=123.453(19)°, V=4713(3) Å3, Mr=867.73, Z=4, Dc=1.223 g/cm3, μ=0.456 mm-1, F(000)=1832, the final R=0.0685 and wR=0.1758 (I > 2σ(I)). The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913×107 g of PNB (mol of Ni)-1 h-1, and the yields of these reactions depend on the nature of the substituent in the aromatic ring.
2016, 35(4): 566-576
doi: 10.14102/j.cnki.0254-5861.2011-0901
Abstract:
Two coordination polymers with 1,4-benzenedicarboxylic acid (H2BDC) ligand, namely,[Tb3(BDC)4.5(H2O)(DMF)2]n (1) and[Tb2(BDC)3(H2O)2(DMF)2]n (2), have been synthesized and characterized. Both compounds crystallize in the triclinic system, space group P1. For compound 1, a=10.8528(5), b=12.2516(5), c=16.9031(7) Å, α=104.462(1), β=93.659(1), γ=101.404(1)°, V=2118.1(2) Å3, Z=2, C42H34N2O21Tb3, Mr=1379.47, Dc=2.163 g/cm3, μ=5.045 mm-1, F(000)=1326, the final R=0.0212 and wR=0.0570 for 8592 observed reflections with I > 2σ(I). For compound 2, a=8.547(1), b=10.170(1), c=11.192(1) Å, α=65.531(1), β=71.886(1), γ=78.796(1)°, V=839.2(2) Å3, Z=1, C30H30N2O16Tb2, Mr=992.40, Dc=1.964 g/cm3, μ=4.257 mm-1, F(000)=482, the final R=0.0220 and wR=0.0649 for 3626 observed reflections with I > 2σ(I). The compounds exhibit different structural topologies depending on the nature of templating agents in the reactions though the templating agents are not incorporated in the final solids. Compound 1 exhibits a three-dimensional (3D) framework based on the rod-shaped terbium-carboxylate building blocks constructed from linear trinuclear Tb3 units. Compound 2 has a 3D framework containing two interpenetrating pcu topological networks based on the 6-connected dinuclear Tb2 secondary building units. Photoluminescence studies show both compounds exhibit typical Tb(Ⅲ) luminescence emissions. An efficient ligand-to-Tb(Ⅲ) energy transfer is observed in the emission spectra for both compounds.
Two coordination polymers with 1,4-benzenedicarboxylic acid (H2BDC) ligand, namely,[Tb3(BDC)4.5(H2O)(DMF)2]n (1) and[Tb2(BDC)3(H2O)2(DMF)2]n (2), have been synthesized and characterized. Both compounds crystallize in the triclinic system, space group P1. For compound 1, a=10.8528(5), b=12.2516(5), c=16.9031(7) Å, α=104.462(1), β=93.659(1), γ=101.404(1)°, V=2118.1(2) Å3, Z=2, C42H34N2O21Tb3, Mr=1379.47, Dc=2.163 g/cm3, μ=5.045 mm-1, F(000)=1326, the final R=0.0212 and wR=0.0570 for 8592 observed reflections with I > 2σ(I). For compound 2, a=8.547(1), b=10.170(1), c=11.192(1) Å, α=65.531(1), β=71.886(1), γ=78.796(1)°, V=839.2(2) Å3, Z=1, C30H30N2O16Tb2, Mr=992.40, Dc=1.964 g/cm3, μ=4.257 mm-1, F(000)=482, the final R=0.0220 and wR=0.0649 for 3626 observed reflections with I > 2σ(I). The compounds exhibit different structural topologies depending on the nature of templating agents in the reactions though the templating agents are not incorporated in the final solids. Compound 1 exhibits a three-dimensional (3D) framework based on the rod-shaped terbium-carboxylate building blocks constructed from linear trinuclear Tb3 units. Compound 2 has a 3D framework containing two interpenetrating pcu topological networks based on the 6-connected dinuclear Tb2 secondary building units. Photoluminescence studies show both compounds exhibit typical Tb(Ⅲ) luminescence emissions. An efficient ligand-to-Tb(Ⅲ) energy transfer is observed in the emission spectra for both compounds.
2016, 35(4): 577-585
doi: 10.14102/j.cnki.0254-5861.2011-0909
Abstract:
Two coordination polymers called[Ni(L)2]n (1) and[Ni(2,2'-bpy)22(H2O)]n (2) (HL=4-benzoimidazol-1-yl-methyl benzoic acid, 2,2'-bpy=2,2'-dipyridine) were synthesized by solvothermal reaction simultaneously and characterized by elemental analyses, thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a=14.673(3), b=10.773(2), c=16.566(3) Å, V=2559.2(8) Å3, Z=4 and F(000)=1160. 2 also crystallizes in monoclinic system, space group C2/c with a=15.404(3), b=12.652(3), c=6.5362(13) Å, V=1246.2(5) Å3, Z=4 and F(000)=712. The bridging L ligand connects the NiⅡ cations into a 2D network in complex 1, while 2 shows a 1D structure formed through the two O atoms of SO42- ions connecting the molecule. The catalytic properties indicate that complex 1 shows good catalytic activities for the cyanosilylation of 4-chlorobenzaldehyde. In addition, fluorescence property of complex 1 which quenches the excitation intensity in solid state was investigated at room temperature.
Two coordination polymers called[Ni(L)2]n (1) and[Ni(2,2'-bpy)22(H2O)]n (2) (HL=4-benzoimidazol-1-yl-methyl benzoic acid, 2,2'-bpy=2,2'-dipyridine) were synthesized by solvothermal reaction simultaneously and characterized by elemental analyses, thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a=14.673(3), b=10.773(2), c=16.566(3) Å, V=2559.2(8) Å3, Z=4 and F(000)=1160. 2 also crystallizes in monoclinic system, space group C2/c with a=15.404(3), b=12.652(3), c=6.5362(13) Å, V=1246.2(5) Å3, Z=4 and F(000)=712. The bridging L ligand connects the NiⅡ cations into a 2D network in complex 1, while 2 shows a 1D structure formed through the two O atoms of SO42- ions connecting the molecule. The catalytic properties indicate that complex 1 shows good catalytic activities for the cyanosilylation of 4-chlorobenzaldehyde. In addition, fluorescence property of complex 1 which quenches the excitation intensity in solid state was investigated at room temperature.
2016, 35(4): 586-590
doi: 10.14102/j.cnki.0254-5861.2011-0910
Abstract:
A new Zn(Ⅱ) complex,[Zn(L)2(phen)(H2O)] (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) Å, β=104.296(2)°, V=1580.0(3) Å3, Z=2, Mr=676.02, Dc=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.
A new Zn(Ⅱ) complex,[Zn(L)2(phen)(H2O)] (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) Å, β=104.296(2)°, V=1580.0(3) Å3, Z=2, Mr=676.02, Dc=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.
2016, 35(4): 591-596
doi: 10.14102/j.cnki.0254-5861.2011-0908
Abstract:
In this work, we synthesized a new two-dimensional Cd(Ⅱ) coordination polymer,[Cd(1,4-NDC)(L)] (1), by using mixed 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) and typical chelating N-donor ligands 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f] [1,10]phenanthroline ligand (L). Compound 1 crystallizes in monoclinic, space group P21/n with a=12.936(5), b=15.245(5), c=13.499(5) Å, β=105.456(5)o, V=2565.9(16) Å3, Z=4, C31H16CdClFN4O4, Mr=675.33, Dc=1.748 g/cm3, F(000)=1344, μ(MoKa)=1.011 mm-1, R=0.0350 and wR=0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd(Ⅱ) atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N-H…O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.
In this work, we synthesized a new two-dimensional Cd(Ⅱ) coordination polymer,[Cd(1,4-NDC)(L)] (1), by using mixed 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) and typical chelating N-donor ligands 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f] [1,10]phenanthroline ligand (L). Compound 1 crystallizes in monoclinic, space group P21/n with a=12.936(5), b=15.245(5), c=13.499(5) Å, β=105.456(5)o, V=2565.9(16) Å3, Z=4, C31H16CdClFN4O4, Mr=675.33, Dc=1.748 g/cm3, F(000)=1344, μ(MoKa)=1.011 mm-1, R=0.0350 and wR=0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd(Ⅱ) atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N-H…O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.
2016, 35(4): 597-604
doi: 10.14102/j.cnki.0254-5861.2011-0884
Abstract:
Two distinct copper coordination polymers, namely[CuⅡ2(2,5-pydc)2(bpp)2]·H2O (1) and Cu2ⅠCuⅡ(2,5-pydc)2(bpp)2 (2) (2,5-pydc=pyridine-2,5-dicarboxylic acid, bpp=1,3-bi(4-pyridyl)propane), have been successfully synthesized through hydrothermal conditions under different temperatures. Single-crystal X-ray structural analysis revealed that both complexes 1 and 2 are 3D frameworks. Complex 1 is an 8-connected 2-fold interpenetrating network based on[Cu(2,5-pydc)]4 molecular building block (MBB), and also can be simplified as a 4-connected net if the Cu(Ⅱ) ion is regarded as an independent node, whereas 2 shows a (4,4)-connected non-interpenetrated framework which contains mixed valence Cu(Ⅰ/Ⅱ) centers. The results demonstrate that temperature plays a significant role in the final structures of the complexes.
Two distinct copper coordination polymers, namely[CuⅡ2(2,5-pydc)2(bpp)2]·H2O (1) and Cu2ⅠCuⅡ(2,5-pydc)2(bpp)2 (2) (2,5-pydc=pyridine-2,5-dicarboxylic acid, bpp=1,3-bi(4-pyridyl)propane), have been successfully synthesized through hydrothermal conditions under different temperatures. Single-crystal X-ray structural analysis revealed that both complexes 1 and 2 are 3D frameworks. Complex 1 is an 8-connected 2-fold interpenetrating network based on[Cu(2,5-pydc)]4 molecular building block (MBB), and also can be simplified as a 4-connected net if the Cu(Ⅱ) ion is regarded as an independent node, whereas 2 shows a (4,4)-connected non-interpenetrated framework which contains mixed valence Cu(Ⅰ/Ⅱ) centers. The results demonstrate that temperature plays a significant role in the final structures of the complexes.
2016, 35(4): 605-614
doi: 10.14102/j.cnki.0254-5861.2011-0898
Abstract:
Two 3D 4-fold interpenetrated metal-organic frameworks,[Mn(L)(bpy)]n (1) and[Cu(HL)(bpy)]n (2) (H3L=4,4',4''-(benzene-1,3,5-triyl-tri(methyleneoxy)) tribenzoic acid, bpy=4,4'-bipyridine), were synthesized under hydrothermal conditions, and characterized by element analyses, IR spectra, thermogravimetric analyses, X-ray powder diffraction and magnetic property studies. The single-crystal X-ray analyses revealed that 1 and 2 are homogeneous. 2 crystallizes in monoclinic, space group Cc with a=26.794(2), b=11.6346(10), c=21.4614(18) Å, β=91.570(2)°, V=6687.9(10) Å3, Z=8, Mr=736.59, Dc=1.463 g·cm-3, μ=0.458 mm-1, Rint=0.0524, F(000)=3040, the final R=0.0844 and wR=0.2266 for 8092 observed reflections (I > 2σ(I)). 2 crystallizes in monoclinic, space group Cc with a=27.609(12), b=11.126(10), c=21.490(9) Å, β=92.131(2)°, V=6597(5) Å3, Z=8, Mr=746.21, Dc=1503 g·cm-3, μ=0.726 mm-1, Rint=0.0542, F(000)=3080, the final R=0.0681 and wR=0.1831 for 6777 observed reflections (I>2σ(I)). Two compounds are 3D[2+2]-type 4-fold interpenetrated frameworks with (63)(69.8) hms topology. The magnetic study of compound 2 shows the presence of weak antiferromagnetic interaction between the CuⅡ ions in 2.
Two 3D 4-fold interpenetrated metal-organic frameworks,[Mn(L)(bpy)]n (1) and[Cu(HL)(bpy)]n (2) (H3L=4,4',4''-(benzene-1,3,5-triyl-tri(methyleneoxy)) tribenzoic acid, bpy=4,4'-bipyridine), were synthesized under hydrothermal conditions, and characterized by element analyses, IR spectra, thermogravimetric analyses, X-ray powder diffraction and magnetic property studies. The single-crystal X-ray analyses revealed that 1 and 2 are homogeneous. 2 crystallizes in monoclinic, space group Cc with a=26.794(2), b=11.6346(10), c=21.4614(18) Å, β=91.570(2)°, V=6687.9(10) Å3, Z=8, Mr=736.59, Dc=1.463 g·cm-3, μ=0.458 mm-1, Rint=0.0524, F(000)=3040, the final R=0.0844 and wR=0.2266 for 8092 observed reflections (I > 2σ(I)). 2 crystallizes in monoclinic, space group Cc with a=27.609(12), b=11.126(10), c=21.490(9) Å, β=92.131(2)°, V=6597(5) Å3, Z=8, Mr=746.21, Dc=1503 g·cm-3, μ=0.726 mm-1, Rint=0.0542, F(000)=3080, the final R=0.0681 and wR=0.1831 for 6777 observed reflections (I>2σ(I)). Two compounds are 3D[2+2]-type 4-fold interpenetrated frameworks with (63)(69.8) hms topology. The magnetic study of compound 2 shows the presence of weak antiferromagnetic interaction between the CuⅡ ions in 2.
2016, 35(4): 615-620
doi: 10.14102/j.cnki.0254-5861.2011-0886
Abstract:
A two-dimensional coordination polymer,[Pb(bmzbc)2]n (1) (Hbmzbc=4-benzimidazole-1-yl-benzoic acid), has been synthesized by the solvothermal reaction of Pb(NO3)2 with Hbmzbc at 120℃ in ethanol solvent. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the orthorhombic system, space group Pccn, with a=12.5801(7), b=20.0795(11), c=9.1830(6) Å, V=2319.6(2) Å3, Z=4, C28H18N4O4Pb, Mr=681.65, Dc=1.952 g/cm3, μ=7.319 mm-1, F(000)=1312, the final R=0.0336 and wR=0.0965 for 1699 observed reflection with I>2σ(I). In 1, the bmzbc-ligands bridge the Pb(Ⅱ) ions to generate a 2-D sheet with (4, 4) topology. The complex exhibits turquoise photoluminescent emission with a maximum at 480 nm upon excitation at 300 nm.
A two-dimensional coordination polymer,[Pb(bmzbc)2]n (1) (Hbmzbc=4-benzimidazole-1-yl-benzoic acid), has been synthesized by the solvothermal reaction of Pb(NO3)2 with Hbmzbc at 120℃ in ethanol solvent. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the orthorhombic system, space group Pccn, with a=12.5801(7), b=20.0795(11), c=9.1830(6) Å, V=2319.6(2) Å3, Z=4, C28H18N4O4Pb, Mr=681.65, Dc=1.952 g/cm3, μ=7.319 mm-1, F(000)=1312, the final R=0.0336 and wR=0.0965 for 1699 observed reflection with I>2σ(I). In 1, the bmzbc-ligands bridge the Pb(Ⅱ) ions to generate a 2-D sheet with (4, 4) topology. The complex exhibits turquoise photoluminescent emission with a maximum at 480 nm upon excitation at 300 nm.
2016, 35(4): 621-632
doi: 10.14102/j.cnki.0254-5861.2011-0899
Abstract:
Three new supramolecular polymers,[(IP)(H2SO4)(H2O)] (1),[(H2SDC)(BPA)] (2) and[Mn(SDC)(IP)2]n (3), have been constructed by three modes (rigid IP, rigid SDC+flexible BPA, rigid IP+rigid SDC). Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π…π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π…π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.
Three new supramolecular polymers,[(IP)(H2SO4)(H2O)] (1),[(H2SDC)(BPA)] (2) and[Mn(SDC)(IP)2]n (3), have been constructed by three modes (rigid IP, rigid SDC+flexible BPA, rigid IP+rigid SDC). Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π…π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π…π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.
2016, 35(4): 633-639
doi: 10.14102/j.cnki.0254-5861.2011-0891
Abstract:
A copper(Ⅱ) complex[LCu2C14]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-(4-fluorophenyl)iminomethyl-8-quinolinoxy]butane (L). X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a=9.387(2), b=9.968(2), c=10.291(2) Å, α=87.532(3), β=63.762(2), γ=86.628(3)°, V=862.1(3) Å3, Z=1, Dc=1.640 Mg/m3, F(000)=428, R=0.0416 and wR=0.1141. Each Cu(Ⅱ) metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper(Ⅱ) complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.
A copper(Ⅱ) complex[LCu2C14]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-(4-fluorophenyl)iminomethyl-8-quinolinoxy]butane (L). X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a=9.387(2), b=9.968(2), c=10.291(2) Å, α=87.532(3), β=63.762(2), γ=86.628(3)°, V=862.1(3) Å3, Z=1, Dc=1.640 Mg/m3, F(000)=428, R=0.0416 and wR=0.1141. Each Cu(Ⅱ) metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper(Ⅱ) complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.
2016, 35(4): 640-644
doi: 10.14102/j.cnki.0254-5861.2011-0991
Abstract:
The novel Schiff base (E)-3-chloro-2-(2-(2-methylbenzylidene)hydrazinyl)pyridine was synthesized and characterized by 1H NMR, MS, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic space group Pbca with a=14.6638(3), b=7.7522(2), c=20.3850(4) Å, V=2317.30(9) Å3, Z=8, R=0.063 and wR=0.1922. The title compound exhibits good antifungal activity against Stemphylium lycopersici (Enjoji) Yamamoto and Fusarium oxysporum sp. cucumebrium.
The novel Schiff base (E)-3-chloro-2-(2-(2-methylbenzylidene)hydrazinyl)pyridine was synthesized and characterized by 1H NMR, MS, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic space group Pbca with a=14.6638(3), b=7.7522(2), c=20.3850(4) Å, V=2317.30(9) Å3, Z=8, R=0.063 and wR=0.1922. The title compound exhibits good antifungal activity against Stemphylium lycopersici (Enjoji) Yamamoto and Fusarium oxysporum sp. cucumebrium.
2016, 35(4): 645-650
doi: 10.14102/j.cnki.0254-5861.2011-0957
Abstract:
4-Methyl-2-(4-methylphenyl)-5-(2-thiazolinyl)-1,3-thiazole, a novel compound, was synthesized by the annulation of 5-hydroxyethylcarbamoyl-4-methyl-2-(4-methylphenyl)-1,3-thiazole with P2S5. 5-Hydroxyethylcarbamoyl-4-methyl-2-(4-methylphenyl)-1,3-thiazole was prepared from the starting material of p-tolunitrile. The newly synthesized compounds were characterized by elemental analysis, IR, NMR (1H, 13C) and MS spectra. Hence, the crystal of the title compound was obtained, and its structure was determined by X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1 with a=7.354(4), b=8.383(4), c=11.543(6) Å, α=76.688(6), β=72.299(6), γ=88.157(6)°, V=659.2(6) Å3, Z=2, Mr=274.39, Dc=1.382 g/cm3, μ=0.386 mm-1, F(000)=288, R=0.0586 and wR=0.1808 for 2984 unique reflections with 2213observed ones (I > 2σ(I)). The title compound was also screened for its antibacterial activities against Bacillus subtilis and Escherichia coli. The result indicates that the target compound presents potential antimicrobial activities, and that the minimum inhibitory concentration (MIC) values of the title compound against the two tested strains are both 62.5 μg/mL.
4-Methyl-2-(4-methylphenyl)-5-(2-thiazolinyl)-1,3-thiazole, a novel compound, was synthesized by the annulation of 5-hydroxyethylcarbamoyl-4-methyl-2-(4-methylphenyl)-1,3-thiazole with P2S5. 5-Hydroxyethylcarbamoyl-4-methyl-2-(4-methylphenyl)-1,3-thiazole was prepared from the starting material of p-tolunitrile. The newly synthesized compounds were characterized by elemental analysis, IR, NMR (1H, 13C) and MS spectra. Hence, the crystal of the title compound was obtained, and its structure was determined by X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1 with a=7.354(4), b=8.383(4), c=11.543(6) Å, α=76.688(6), β=72.299(6), γ=88.157(6)°, V=659.2(6) Å3, Z=2, Mr=274.39, Dc=1.382 g/cm3, μ=0.386 mm-1, F(000)=288, R=0.0586 and wR=0.1808 for 2984 unique reflections with 2213observed ones (I > 2σ(I)). The title compound was also screened for its antibacterial activities against Bacillus subtilis and Escherichia coli. The result indicates that the target compound presents potential antimicrobial activities, and that the minimum inhibitory concentration (MIC) values of the title compound against the two tested strains are both 62.5 μg/mL.
2016, 35(4): 651-655
doi: 10.14102/j.cnki.0254-5861.2011-1022
Abstract:
The title compound 8-chloro-3-((4-chlorobenzyl)thio)-[1,2,4]triazolo[4,3-a]pyridine was prepared from 1-chloro-4-(chloromethyl)benzene and 8-chloro-[1,2,4]triazolo[4,3-a]pyridine-3(2H)-thione in the presence of NaOH, and its structure was determined by X-ray diffraction analysis. The crystal is of triclinic system, space group P1 with a=6.8264(6), b=7.5890(4), c=13.0960(7) Å, α=93.447(4), β=98.772(6), γ=92.615(6)°, V=668.26(8) Å3, Z=2, the final R=0.035 and wR=0.09 for 2259 observed reflections with I > 2σ(I). The preliminary biological test showed that the title compound has activities against Stemphylium lycopersici (Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea with inhibitory to be 51.19%, 62.02% and 15.56%, respectively.
The title compound 8-chloro-3-((4-chlorobenzyl)thio)-[1,2,4]triazolo[4,3-a]pyridine was prepared from 1-chloro-4-(chloromethyl)benzene and 8-chloro-[1,2,4]triazolo[4,3-a]pyridine-3(2H)-thione in the presence of NaOH, and its structure was determined by X-ray diffraction analysis. The crystal is of triclinic system, space group P1 with a=6.8264(6), b=7.5890(4), c=13.0960(7) Å, α=93.447(4), β=98.772(6), γ=92.615(6)°, V=668.26(8) Å3, Z=2, the final R=0.035 and wR=0.09 for 2259 observed reflections with I > 2σ(I). The preliminary biological test showed that the title compound has activities against Stemphylium lycopersici (Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea with inhibitory to be 51.19%, 62.02% and 15.56%, respectively.
2016, 35(4): 656-662
doi: 10.14102/j.cnki.0254-5861.2011-1111
Abstract:
The important synthetic precursor (Ⅲ), 1-(prop-2-yn-1-yl)-7,8-dihydro-1Hbenzo[d] [1,3]thiazine-2,5(4H,6H)-dione (C11H11NO2S), was prepared through a three-component reaction, which was further transferred into cytotoxic triazoles by alkylation and "click" synthesis in satisfactory yields of 87%~95%. Their structures were characterized by IR, H-RESI-MS and NMR analysis. Meanwhile, the crystal of Ⅲ was obtained and determined by X-ray single-crystal diffraction. Crystal data:orthorhombic system, space group P212121, a=5.189(4), b=8.661(6), c=23.498(17) Å, V=1056.2(13) Å3, Z=4, F(000)=464, Dc=1.392 g/cm3, μ=0.284 mm-1, R=0.0637 and wR=0.1668 for 8182 independent reflections (Rint=0.1580) and 2166 observed ones (I > 2(I)).
The important synthetic precursor (Ⅲ), 1-(prop-2-yn-1-yl)-7,8-dihydro-1Hbenzo[d] [1,3]thiazine-2,5(4H,6H)-dione (C11H11NO2S), was prepared through a three-component reaction, which was further transferred into cytotoxic triazoles by alkylation and "click" synthesis in satisfactory yields of 87%~95%. Their structures were characterized by IR, H-RESI-MS and NMR analysis. Meanwhile, the crystal of Ⅲ was obtained and determined by X-ray single-crystal diffraction. Crystal data:orthorhombic system, space group P212121, a=5.189(4), b=8.661(6), c=23.498(17) Å, V=1056.2(13) Å3, Z=4, F(000)=464, Dc=1.392 g/cm3, μ=0.284 mm-1, R=0.0637 and wR=0.1668 for 8182 independent reflections (Rint=0.1580) and 2166 observed ones (I > 2(I)).
