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2015 Volume 34 Issue 1
2015, 34(1): 7-14
doi: 10.14102/j.cnki.0254-5861.2011-0476
Abstract:
The mechanism of cycloaddition reaction between singlet state H2Ge=Ge: and acetaldehyde has been investigated with the MP2/6-311++G** method. From the potential energy profile, it could be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. As the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the π orbital of acetaldehyde form a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetaldehyde to give an intermediate. Because the Ge atom in intermediate exhibits sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring germylene makes it isomerize to a twisted four-membered ring product.
The mechanism of cycloaddition reaction between singlet state H2Ge=Ge: and acetaldehyde has been investigated with the MP2/6-311++G** method. From the potential energy profile, it could be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. As the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the π orbital of acetaldehyde form a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetaldehyde to give an intermediate. Because the Ge atom in intermediate exhibits sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring germylene makes it isomerize to a twisted four-membered ring product.
2015, 34(1): 15-25
doi: 10.14102/j.cnki.0254-5861.2011-0423
Abstract:
1,2-Benzothiazine derivatives methyl 3-methoxy-4-oxo-3,4-dihydro-2H-benzo[e][1,2]thiazine-3-carboxylate 1,1-dioxide (1) and methyl 2-ethyl-3-hydroxy-4-oxo-3,4-dihydro-2H-benzo[e][1,2]thiazine-3-carboxylate 1,1-dioxide (2) were synthesized, and characterized by spectroscopic techniques; 1H-NMR and infrared (IR) spectroscopy. Crystals of 1 and 2 were grown by slow evaporation of methanol and ethyl acetate, respectively and their crystal structures were investigated by single-crystal X-ray diffraction analysis. Geometric properties were calculated by the B3LYP method of density functional theory (DFT) at the 6-31G+(d) basis set to compare with the experimental data. Simulated properties were found in strong agreement with the experimental ones. Intermolecular forces have also been modeled in order to investigate the strength of packing and strong hydrogen bonding was observed in both compounds 1 and 2. Electronic properties such as Ionization Potential (IP), Electron Affinities (EA) and coefficients of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of com-pounds 1 and 2 were simulated for the first time.
1,2-Benzothiazine derivatives methyl 3-methoxy-4-oxo-3,4-dihydro-2H-benzo[e][1,2]thiazine-3-carboxylate 1,1-dioxide (1) and methyl 2-ethyl-3-hydroxy-4-oxo-3,4-dihydro-2H-benzo[e][1,2]thiazine-3-carboxylate 1,1-dioxide (2) were synthesized, and characterized by spectroscopic techniques; 1H-NMR and infrared (IR) spectroscopy. Crystals of 1 and 2 were grown by slow evaporation of methanol and ethyl acetate, respectively and their crystal structures were investigated by single-crystal X-ray diffraction analysis. Geometric properties were calculated by the B3LYP method of density functional theory (DFT) at the 6-31G+(d) basis set to compare with the experimental data. Simulated properties were found in strong agreement with the experimental ones. Intermolecular forces have also been modeled in order to investigate the strength of packing and strong hydrogen bonding was observed in both compounds 1 and 2. Electronic properties such as Ionization Potential (IP), Electron Affinities (EA) and coefficients of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of com-pounds 1 and 2 were simulated for the first time.
2015, 34(1): 26-32
doi: 10.14102/j.cnki.0254-5861.2011-0457
Abstract:
Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu(OAc)2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a (C10H9N5O4) crystallizes in the triclinic system, space group P1 with a=5.0894(9), b=8.9834(13), c=13.089(2)Å, α=83.041(7), β=80.256(7), γ=87.296(8)°, V=585.24(16)Å3, Z=2, Mr=263.22, crystal size (mm)=0.37×0.20×0.18, (I>2σ(I))=8557, 2493, 1229, Rint=0.057. Compound 1b (C12H13N5O4) crystallizes in the monoclinic system, space group P21/c with a=6.8854(5), b=21.783(2), c=9.3986(8)Å, β=93.239(4)°, V=1407.4(2)Å3, Z=4, Mr=291.27, crystal size (mm)=0.38×0.22×0.20, (I>2σ(I))=11842, 3172, 1866, Rint=0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.
Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu(OAc)2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a (C10H9N5O4) crystallizes in the triclinic system, space group P1 with a=5.0894(9), b=8.9834(13), c=13.089(2)Å, α=83.041(7), β=80.256(7), γ=87.296(8)°, V=585.24(16)Å3, Z=2, Mr=263.22, crystal size (mm)=0.37×0.20×0.18, (I>2σ(I))=8557, 2493, 1229, Rint=0.057. Compound 1b (C12H13N5O4) crystallizes in the monoclinic system, space group P21/c with a=6.8854(5), b=21.783(2), c=9.3986(8)Å, β=93.239(4)°, V=1407.4(2)Å3, Z=4, Mr=291.27, crystal size (mm)=0.38×0.22×0.20, (I>2σ(I))=11842, 3172, 1866, Rint=0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.
2015, 34(1): 33-40
doi: 10.14102/j.cnki.0254-5861.2011-0447
Abstract:
The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid (C11H9ClN2O2, HL) (1) and [Cu(L)2(H2O)] (2) were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1 (C11H9ClN2O2) crystallizes in the monoclinic system, space group P21/n with a=7.249(3), b=20.515(10), c=7.249(3), β=96.30°, V=1071.6(9)Å3, Z=4, Mr=236.65, Dc=1.467 g/cm3, F(000)=488, GOOF=1.029, μ=0.341 mm-1, the final R=0.0736 and wR=0.1966 for 1500 observed reflections with I>2σ(I). Compound 2 (C22H18Cl2CuN4O5) crystallizes in the monoclinic system, space group P21/c with a=7.2931(6), b=24.548(2), c=13.2726(11), β=99.4040(10)°, V=2344.2(3)Å3, Z=4, Mr=552.84, Dc=1.566 g/cm3, F(000)=1124, GOOF=1.050, μ=1.201 mm-1, the final R=0.0376 and wR=0.1000 for 3626 observed reflections with I>2σ(I). 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria (S. aureus, C. albicans and B. subtilis) and gram negative bacteria (E. coli and P. aeruginosa) have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.
The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid (C11H9ClN2O2, HL) (1) and [Cu(L)2(H2O)] (2) were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1 (C11H9ClN2O2) crystallizes in the monoclinic system, space group P21/n with a=7.249(3), b=20.515(10), c=7.249(3), β=96.30°, V=1071.6(9)Å3, Z=4, Mr=236.65, Dc=1.467 g/cm3, F(000)=488, GOOF=1.029, μ=0.341 mm-1, the final R=0.0736 and wR=0.1966 for 1500 observed reflections with I>2σ(I). Compound 2 (C22H18Cl2CuN4O5) crystallizes in the monoclinic system, space group P21/c with a=7.2931(6), b=24.548(2), c=13.2726(11), β=99.4040(10)°, V=2344.2(3)Å3, Z=4, Mr=552.84, Dc=1.566 g/cm3, F(000)=1124, GOOF=1.050, μ=1.201 mm-1, the final R=0.0376 and wR=0.1000 for 3626 observed reflections with I>2σ(I). 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria (S. aureus, C. albicans and B. subtilis) and gram negative bacteria (E. coli and P. aeruginosa) have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.
2015, 34(1): 41-48
doi: 10.14102/j.cnki.0254-5861.2011-0425
Abstract:
One new benzimidazole derivative copper(Ⅱ) complex 1 (C10H6CuN2, Mr=217.71) has been synthesized and characterized by FT-IR and X-ray single-crystal diffraction. It crystallizes in orthorhombic, space group Pbcn with a=17.417(2), b=8.9963(8), c=11.3432(9)Å, V=1777.3(3)Å3, Z=8, μ(MoKα)=2.403, F(000)=872, Dc=1.627 g/cm3. The final R=0.0598 for 1153 observed reflections with I>2σ(I) and wR=0.17 for all data. The in vitro anti-cancer activities of 1, CuCl2 and the benzimidazole ligand L were investigated using human cervical (Hela) and hepatocellular carcinoma (Hep-G2) cancer cell lines. The copper(Ⅱ) complex can greatly inhibit the cell proliferation and show stronger cytotoxic activities against the tested cancer cell lines than both the ligand and copper(Ⅱ) salt.
One new benzimidazole derivative copper(Ⅱ) complex 1 (C10H6CuN2, Mr=217.71) has been synthesized and characterized by FT-IR and X-ray single-crystal diffraction. It crystallizes in orthorhombic, space group Pbcn with a=17.417(2), b=8.9963(8), c=11.3432(9)Å, V=1777.3(3)Å3, Z=8, μ(MoKα)=2.403, F(000)=872, Dc=1.627 g/cm3. The final R=0.0598 for 1153 observed reflections with I>2σ(I) and wR=0.17 for all data. The in vitro anti-cancer activities of 1, CuCl2 and the benzimidazole ligand L were investigated using human cervical (Hela) and hepatocellular carcinoma (Hep-G2) cancer cell lines. The copper(Ⅱ) complex can greatly inhibit the cell proliferation and show stronger cytotoxic activities against the tested cancer cell lines than both the ligand and copper(Ⅱ) salt.
2015, 34(1): 49-55
doi: 10.14102/j.cnki.0254-5861.2011-0407
Abstract:
A new kind of Fe-Si adsorbent was synthesized by iron oxide and diatomite after calcining and hydrothermal process. The influences of the initial Cu2+ concentration, pH and adsorption time on the Cu2+ removal efficiency were discussed. Three adsorption empirical kinetics equations and two thermodynamics equations were used to simulate the adsorption process. The microstructures of newly developed copper removal materials and properties of copper removal are characterized in details by SEM and EDS. Adsorption mechanism of the adsorbent was discussed. The suitable pH value for Cu2+ removal is 5.0 to 6.0 and the adsorption capacity increases with increasing the initial Cu2+ concentration. The adsorption kinetics of the adsorbent could be better described by pseudo second order kinetic model, whereas the adsorption isotherms highly conform to the Freundlich equation. The main crystalline phase of the adsorbent is Fe(SiO3) which can build porous structures conducive to the Cu2+ adsorption.
A new kind of Fe-Si adsorbent was synthesized by iron oxide and diatomite after calcining and hydrothermal process. The influences of the initial Cu2+ concentration, pH and adsorption time on the Cu2+ removal efficiency were discussed. Three adsorption empirical kinetics equations and two thermodynamics equations were used to simulate the adsorption process. The microstructures of newly developed copper removal materials and properties of copper removal are characterized in details by SEM and EDS. Adsorption mechanism of the adsorbent was discussed. The suitable pH value for Cu2+ removal is 5.0 to 6.0 and the adsorption capacity increases with increasing the initial Cu2+ concentration. The adsorption kinetics of the adsorbent could be better described by pseudo second order kinetic model, whereas the adsorption isotherms highly conform to the Freundlich equation. The main crystalline phase of the adsorbent is Fe(SiO3) which can build porous structures conducive to the Cu2+ adsorption.
2015, 34(1): 56-68
doi: 10.14102/j.cnki.0254-5861.2011-0442
Abstract:
V-doped TiO2 nanoparticles (NPs) as dye adsorbents are synthesized by the co-precipitation method and characterized by X-ray powder diffraction, transmission electron microscope, N2 adsorption at 77 K, and X-ray photoelectron spectroscopy. The adsorption of methylene blue (MB) on the V-doped TiO2 NPs is studied in detail by varying the calcination temperature and V doping amount of the adsorbent, adsorbate concentration, adsorbent dosage, agitation rate, reaction temperature, and pH. The comparison of dye adsorption on V-doped TiO2 and parent TiO2 demonstrates that the adsorptive activity of TiO2 can be improved by V doping. The enhanced adsorptive performance can be attributed to the tremendous changes in texture, structure, and surface morphology of adsorbent. The adsorption kinetic analysis shows that the adsorption follows the pseudo-second order kinetics. The apparent activation energy for adsorption is calculated by Arrhenius formula to be 37.6 kJ·mol-1, indicating that the adsorption is controlled by both of the diffusion and interfacial adsorption steps. The adsorption data are analyzed using Langmuir and Freundlich isotherms and the results indicate that the Langmuir model provides better correlation of the experimental data. The results conclusively show that the adsorption of MB is a spontaneous behavior and endothermic reaction with the ΔH value of 17.60 kJ·mol-1.
V-doped TiO2 nanoparticles (NPs) as dye adsorbents are synthesized by the co-precipitation method and characterized by X-ray powder diffraction, transmission electron microscope, N2 adsorption at 77 K, and X-ray photoelectron spectroscopy. The adsorption of methylene blue (MB) on the V-doped TiO2 NPs is studied in detail by varying the calcination temperature and V doping amount of the adsorbent, adsorbate concentration, adsorbent dosage, agitation rate, reaction temperature, and pH. The comparison of dye adsorption on V-doped TiO2 and parent TiO2 demonstrates that the adsorptive activity of TiO2 can be improved by V doping. The enhanced adsorptive performance can be attributed to the tremendous changes in texture, structure, and surface morphology of adsorbent. The adsorption kinetic analysis shows that the adsorption follows the pseudo-second order kinetics. The apparent activation energy for adsorption is calculated by Arrhenius formula to be 37.6 kJ·mol-1, indicating that the adsorption is controlled by both of the diffusion and interfacial adsorption steps. The adsorption data are analyzed using Langmuir and Freundlich isotherms and the results indicate that the Langmuir model provides better correlation of the experimental data. The results conclusively show that the adsorption of MB is a spontaneous behavior and endothermic reaction with the ΔH value of 17.60 kJ·mol-1.
2015, 34(1): 69-76
doi: 10.14102/j.cnki.0254-5861.2011-0445
Abstract:
Three novel dehydroabietate oxime derivatives were synthesized from dehydro-abietic acid and their crystal structures were determined by X-ray crystallographic techniques. All of these 12-oxime dehydroabietic acid derivatives crystallize in orthorhombic system, space group P212121. In the structures, rings A and B exhibit chair and half-chair configurations, respectively and form trans ring junction with two methyl groups (C(19) and C(20)) in the axis positions. The oxime groups have E conformations. Comparison of conformations reveals subtle differences principally in ring B due to the modification in C(12). The E-acetaldehyde oxime derivative 2c showed distinct BKα gate-opening activity with an ionic current increase of 164% at 30 μM versus the control current.
Three novel dehydroabietate oxime derivatives were synthesized from dehydro-abietic acid and their crystal structures were determined by X-ray crystallographic techniques. All of these 12-oxime dehydroabietic acid derivatives crystallize in orthorhombic system, space group P212121. In the structures, rings A and B exhibit chair and half-chair configurations, respectively and form trans ring junction with two methyl groups (C(19) and C(20)) in the axis positions. The oxime groups have E conformations. Comparison of conformations reveals subtle differences principally in ring B due to the modification in C(12). The E-acetaldehyde oxime derivative 2c showed distinct BKα gate-opening activity with an ionic current increase of 164% at 30 μM versus the control current.
2015, 34(1): 77-81
doi: 10.14102/j.cnki.0254-5861.2011-0424
Abstract:
The title compound 17(S)-methyl-13β-hydroxyl-14(R),20(S)-epoxy-pregn-4-en-3-one was synthesized by an improved tandem reaction, and its structure was determined by IR, NMR, HR MS and X-ray single-crystal diffraction. The crystal belongs to orthorhombic, space group P212121 with a=10.55248(15), b=12.14700(16), c=14.56841(18)Å, V=1867.39(4)Å3, Z=4, Dc=1.175 g/cm3, μ=0.604 mm-1, F(000)=720, the final R=0.0400 and wR=0.1072 for 3610 observed reflections with I>2σ(I).
The title compound 17(S)-methyl-13β-hydroxyl-14(R),20(S)-epoxy-pregn-4-en-3-one was synthesized by an improved tandem reaction, and its structure was determined by IR, NMR, HR MS and X-ray single-crystal diffraction. The crystal belongs to orthorhombic, space group P212121 with a=10.55248(15), b=12.14700(16), c=14.56841(18)Å, V=1867.39(4)Å3, Z=4, Dc=1.175 g/cm3, μ=0.604 mm-1, F(000)=720, the final R=0.0400 and wR=0.1072 for 3610 observed reflections with I>2σ(I).
2015, 34(1): 82-86
doi: 10.14102/j.cnki.0254-5861.2011-0436
Abstract:
The title compound (S)-N-(2-oxoazepan-3-yl)biphenyl-4-carboxamide (C19H20N2O2, Mr=308.37) was synthesized by the reaction of (S)-α-amino-Σ-caprolactam with 4-phenyl-benzoyl chloride. Its chemical structure was determined by 1H NMR, 13C NMR, H RMS and X-ray single-crystal diffraction. The crystal belongs to the triclinic system, space group P1 with a=8.2650(17), b=13.774(3), c=15.109(3)Å, β=90.20(3)°, V=1645.6(6)Å3, Z=4, Dc=1.245 g/cm3, μ=0.081 mm-1, F(000)=656, R=0.0756 and wR=0.1491 for 5964 observed reflections with I>2σ(I). The title compound was also used to prepare polyamide.
The title compound (S)-N-(2-oxoazepan-3-yl)biphenyl-4-carboxamide (C19H20N2O2, Mr=308.37) was synthesized by the reaction of (S)-α-amino-Σ-caprolactam with 4-phenyl-benzoyl chloride. Its chemical structure was determined by 1H NMR, 13C NMR, H RMS and X-ray single-crystal diffraction. The crystal belongs to the triclinic system, space group P1 with a=8.2650(17), b=13.774(3), c=15.109(3)Å, β=90.20(3)°, V=1645.6(6)Å3, Z=4, Dc=1.245 g/cm3, μ=0.081 mm-1, F(000)=656, R=0.0756 and wR=0.1491 for 5964 observed reflections with I>2σ(I). The title compound was also used to prepare polyamide.
2015, 34(1): 87-94
doi: 10.14102/j.cnki.0254-5861.2011-0403
Abstract:
A tetranuclear erbium complex with pyridine-2,4,6-tricarboxylic acid (H3ptc), [Er4(ptc)4(H2O)18]·6H2O (1), has been synthesized by hydrothermal method. The complex crystallizes in triclinic system, space group P1, with a=7.620(2), b=10.459(3), c=17.418(5)Å, α=92.351(5), β=92.080(5), γ=95.627(4)°, V=1379.1(7)Å3 and Z=2. One Er(Ⅲ) cation is eight-coordinated and the other is nine-coordinated. The complex exhibits characteristic luminescence of erbium cation in near-infrared region upon the excitation of UV-rays. Furthermore, a three-dimensional supramolecular complex was formed by weak hydrogen bonds among the tetranuclear units.
A tetranuclear erbium complex with pyridine-2,4,6-tricarboxylic acid (H3ptc), [Er4(ptc)4(H2O)18]·6H2O (1), has been synthesized by hydrothermal method. The complex crystallizes in triclinic system, space group P1, with a=7.620(2), b=10.459(3), c=17.418(5)Å, α=92.351(5), β=92.080(5), γ=95.627(4)°, V=1379.1(7)Å3 and Z=2. One Er(Ⅲ) cation is eight-coordinated and the other is nine-coordinated. The complex exhibits characteristic luminescence of erbium cation in near-infrared region upon the excitation of UV-rays. Furthermore, a three-dimensional supramolecular complex was formed by weak hydrogen bonds among the tetranuclear units.
2015, 34(1): 95-102
doi: 10.14102/j.cnki.0254-5861.2011-404
Abstract:
Reactions of 2-(2-benzoimidazolyl) acetonitrile and NaN3 with ZnSO4 or ZnCl2 in the presence of nicotinic acid in the mixture of EtOH/H2O afforded a mononuclear compound [Zn(L1)2] (1) and a 1-D polymer [Zn(L1)Cl]n (2), respectively (L1=5-[(benzoimidazolyl) methyl]-1H-tetrazolate). However, in the similar condition except that imidazole was added instead of nicotinic acid, the reaction afforded a 1-D compound [Zn(L1)2]n (3) featuring triply helical chains via the π-π stacking of ligands. They are characterized by elemental analysis and IR, and their structures have been determined by X-ray crystallography. Thermal stability of these compounds was measured by TGA and their luminescent properties were investigated at room temperature.
Reactions of 2-(2-benzoimidazolyl) acetonitrile and NaN3 with ZnSO4 or ZnCl2 in the presence of nicotinic acid in the mixture of EtOH/H2O afforded a mononuclear compound [Zn(L1)2] (1) and a 1-D polymer [Zn(L1)Cl]n (2), respectively (L1=5-[(benzoimidazolyl) methyl]-1H-tetrazolate). However, in the similar condition except that imidazole was added instead of nicotinic acid, the reaction afforded a 1-D compound [Zn(L1)2]n (3) featuring triply helical chains via the π-π stacking of ligands. They are characterized by elemental analysis and IR, and their structures have been determined by X-ray crystallography. Thermal stability of these compounds was measured by TGA and their luminescent properties were investigated at room temperature.
2015, 34(1): 103-109
doi: 10.14102/j.cnki.0254-5861.2011-0408
Abstract:
A new Eu(Ⅲ) complex from 2,2'-bipyridine (2,2'-bipy) and 1,3,5-triazine-2-4,6-tri(L-alanine) (H3L), {[Eu(L)(2,2'-bipy)](H2O)}n (1), has been synthesized and characterized. The X-ray structure analysis reveals that 1 is an infinite one-dimensional chain-like coordination polymer consisting of dinuclear lanthanide building blocks. The 1D chains are further assembled into a 2D supramolecular architecture through π…π interaction among chains. Crystal data for 1: EuC22H25N8O7, triclinic, space group P1 a=11.3965(1), b=11.5112(6), c=12.0404(1)Å, α=61.970(11), β=86.698(15), γ=65.254(12)°, V=1247.0(2)Å3 and Z=2. Solid-state photolumines-scence property of 1 was investigated, which exhibited remarkable red luminescence emissions with high quantum yield up to 37%.
A new Eu(Ⅲ) complex from 2,2'-bipyridine (2,2'-bipy) and 1,3,5-triazine-2-4,6-tri(L-alanine) (H3L), {[Eu(L)(2,2'-bipy)](H2O)}n (1), has been synthesized and characterized. The X-ray structure analysis reveals that 1 is an infinite one-dimensional chain-like coordination polymer consisting of dinuclear lanthanide building blocks. The 1D chains are further assembled into a 2D supramolecular architecture through π…π interaction among chains. Crystal data for 1: EuC22H25N8O7, triclinic, space group P1 a=11.3965(1), b=11.5112(6), c=12.0404(1)Å, α=61.970(11), β=86.698(15), γ=65.254(12)°, V=1247.0(2)Å3 and Z=2. Solid-state photolumines-scence property of 1 was investigated, which exhibited remarkable red luminescence emissions with high quantum yield up to 37%.
2015, 34(1): 110-116
doi: 10.14102/j.cnki.0254-5861.2011-0413
Abstract:
The dual ligand system of V-shaped 5-(4-carboxy-2-nitrophenoxy)-isophthalic acid (Hcn-H2ipa) and dipyridy-type molecules produces two new coordination polymers: {[Ni(cn-Hipa)(bpa)(H2O)3]·1.5H2O}n 1 and {[Cu(Hcn-ipa)(ppe)2]}n 2 (bpa=1,2-bis(4-pyrid-yl)ethane, and ppe=trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene). Two complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, and thermogravimetric analysis (TGA). Complex 1 is of monoclinic system, space group C2 with a=25.936(3), b=7.6100(10), c=16.558(2)Å, β=105.9470(10)°, V=3142.4(7)Å3, Dc=1.415 g/cm3, Mr=669.23, Z=4, F(000)=1388, μ=0.687 mm-1, the final R=0.0397 and wR=0.0967 for 12070 observed reflections with I>2σ(I). Complex 2 belongs to the triclinic system, space group P1 with a=10.165(5), b=14.946(7), c=15.506(11)Å, α=106.461(7), β=102.454(8), γ=107.861(5)°, V=2029(2)Å3, Dc=1.266 g/cm3, Mr=773.20, Z=2, F(000)=794, μ=0.595 mm-1, the final R=0.0538 and wR=0.1378 for 15488 observed reflections with I>2σ(I). Two complexes show that the 1D polymeric chains are cohered together by extensive H-bonds to complete stable supramolecular microporous frameworks.
The dual ligand system of V-shaped 5-(4-carboxy-2-nitrophenoxy)-isophthalic acid (Hcn-H2ipa) and dipyridy-type molecules produces two new coordination polymers: {[Ni(cn-Hipa)(bpa)(H2O)3]·1.5H2O}n 1 and {[Cu(Hcn-ipa)(ppe)2]}n 2 (bpa=1,2-bis(4-pyrid-yl)ethane, and ppe=trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene). Two complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, and thermogravimetric analysis (TGA). Complex 1 is of monoclinic system, space group C2 with a=25.936(3), b=7.6100(10), c=16.558(2)Å, β=105.9470(10)°, V=3142.4(7)Å3, Dc=1.415 g/cm3, Mr=669.23, Z=4, F(000)=1388, μ=0.687 mm-1, the final R=0.0397 and wR=0.0967 for 12070 observed reflections with I>2σ(I). Complex 2 belongs to the triclinic system, space group P1 with a=10.165(5), b=14.946(7), c=15.506(11)Å, α=106.461(7), β=102.454(8), γ=107.861(5)°, V=2029(2)Å3, Dc=1.266 g/cm3, Mr=773.20, Z=2, F(000)=794, μ=0.595 mm-1, the final R=0.0538 and wR=0.1378 for 15488 observed reflections with I>2σ(I). Two complexes show that the 1D polymeric chains are cohered together by extensive H-bonds to complete stable supramolecular microporous frameworks.
2015, 34(1): 117-122
doi: 10.14102/j.cnki.0254-5861.2011-0419
Abstract:
A three-dimensional cobalt coordination polymer [Co(IMPAA)2]n (1, HIMPAA=(2E)-3-[4-(1H-imidazol-1-ylmethyl)phenyl]acrylic acid) was synthesized with ozagrel and structurally characterized by element analysis, IR, PXRD, TGA and X-ray diffraction. Complex 1 is of monoclinic system, space group P21 with a=5.136(4), b=25.577(19), c=8.174(6)Å, V=1078.6(14)Å3, Mr=513.41, Z=2, Dc=1.581 g/cm3, F(000)=686, μ=0.840 mm-1, S=1.119, Rint=0.0637 and wR=0.1456. In complex 1, four IMPAA- and four Co(Ⅱ) ions form a S-shaped 52-membered macrocycle [Co4(IMPAA)4]4+. Two carboxlate oxygen atoms link the macrocycles to form a one-dimensional chain. IMPAA- ligands bridge one-dimensional chains to yield a novel three-dimensional metal-organic framework (MOFs). The complex is stable up to 350℃.
A three-dimensional cobalt coordination polymer [Co(IMPAA)2]n (1, HIMPAA=(2E)-3-[4-(1H-imidazol-1-ylmethyl)phenyl]acrylic acid) was synthesized with ozagrel and structurally characterized by element analysis, IR, PXRD, TGA and X-ray diffraction. Complex 1 is of monoclinic system, space group P21 with a=5.136(4), b=25.577(19), c=8.174(6)Å, V=1078.6(14)Å3, Mr=513.41, Z=2, Dc=1.581 g/cm3, F(000)=686, μ=0.840 mm-1, S=1.119, Rint=0.0637 and wR=0.1456. In complex 1, four IMPAA- and four Co(Ⅱ) ions form a S-shaped 52-membered macrocycle [Co4(IMPAA)4]4+. Two carboxlate oxygen atoms link the macrocycles to form a one-dimensional chain. IMPAA- ligands bridge one-dimensional chains to yield a novel three-dimensional metal-organic framework (MOFs). The complex is stable up to 350℃.
2015, 34(1): 123-132
doi: 10.14102/j.cnki.0254-5861.2011-0428
Abstract:
Two novel metal-organic coordination compounds with molecular structures of {[Co(TMBC)4Cl2]·2H2O} (1) and {[Ni(TMBC)4Cl2]·2H2O} (2) (TMBC=4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitrile), have been synthesized under hydrothermal conditions of CoCl2·6H2O and NiCl2·6H2O with 4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitrile, respectively. Both compounds crystallize in triclinic systems, space group P1. They are characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy and TGA. Moreover, their electrochemical behaviors have also been studied in different electrolyte solutions, respectively.
Two novel metal-organic coordination compounds with molecular structures of {[Co(TMBC)4Cl2]·2H2O} (1) and {[Ni(TMBC)4Cl2]·2H2O} (2) (TMBC=4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitrile), have been synthesized under hydrothermal conditions of CoCl2·6H2O and NiCl2·6H2O with 4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitrile, respectively. Both compounds crystallize in triclinic systems, space group P1. They are characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy and TGA. Moreover, their electrochemical behaviors have also been studied in different electrolyte solutions, respectively.
2015, 34(1): 133-139
doi: 10.14102/j.cnki.0254-5861.2011-0430
Abstract:
A novel coordination polymer [Ba2(AQTC)(H2O)3]n (1, H4AQTC=anthraquinone-1,4,5,8-tetracarboxylic acid) has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Two quinone oxygen atoms and all carboxylate oxygen atoms of AQTC4- are involved in coordination. Two equivalent barium ions are mainly linked by carboxylate oxygen atoms into a dimer. Neighbouring dimers are further connected by the AQTC4- ligand through carboxylate oxygen atom, leading to a 1-D chain structure. Every two adjacent chains are mainly further connected by face carboxylate oxygen atoms and water molecule, generating a two-dimensional layer structure. Such 2-D layer structures are connected with O(6) and O(6C) atoms from water molecules to form a 3-D structure. In addition, luminescent properties of 1 are also investigated.
A novel coordination polymer [Ba2(AQTC)(H2O)3]n (1, H4AQTC=anthraquinone-1,4,5,8-tetracarboxylic acid) has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Two quinone oxygen atoms and all carboxylate oxygen atoms of AQTC4- are involved in coordination. Two equivalent barium ions are mainly linked by carboxylate oxygen atoms into a dimer. Neighbouring dimers are further connected by the AQTC4- ligand through carboxylate oxygen atom, leading to a 1-D chain structure. Every two adjacent chains are mainly further connected by face carboxylate oxygen atoms and water molecule, generating a two-dimensional layer structure. Such 2-D layer structures are connected with O(6) and O(6C) atoms from water molecules to form a 3-D structure. In addition, luminescent properties of 1 are also investigated.
2015, 34(1): 140-146
doi: 10.14102/j.cnki.0254-5861.2011-0444
Abstract:
Two novel silver(Ⅰ) complexes {[Ag(OTf)(PPh3)(4,4'-bipy)]}∞ (1) and {[Ag2-(OTf)2(dppb)3](CH3CN)4}∞ (2) (OTf=trifluoromethanesulfonate, PPh3=triphenylphophine, 4,4'-bipy=4,4'-bipyridine, dppb=bis(diphenylphosphino)butane) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a=19.259(2), b=9.85070(12), c=16.3827(17)Å, V=3108.0(5)Å3, C29H23F3N2O3PSAg, Mr=675.39, Z=4, Dc=1.443 g/cm3, F(000)=1360, μ=0.816 mm-1, the final R=0.0675 and wR=0.1722 for 3662 observed reflections (I>2σ(I)). Complex 2 crystallizes in triclinic, space group P1 with a=12.9370(11), b=13.5261(13), c=16.4539(15)Å, α=106.7120(10), β=97.3830(10), γ=113.027(2)°, V=2441.2(4)Å3, C94H96F6N4O6P6S2Ag2, Mr=1957.43, Z=1, Dc=1.331 g/cm3, F(000)=1006, μ=0.605 mm-1, the final R=0.0717 and wR=0.1795 for 5128 observed reflections (I>2σ(I)). Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf anion, two N atoms from two 4,4'-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.
Two novel silver(Ⅰ) complexes {[Ag(OTf)(PPh3)(4,4'-bipy)]}∞ (1) and {[Ag2-(OTf)2(dppb)3](CH3CN)4}∞ (2) (OTf=trifluoromethanesulfonate, PPh3=triphenylphophine, 4,4'-bipy=4,4'-bipyridine, dppb=bis(diphenylphosphino)butane) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a=19.259(2), b=9.85070(12), c=16.3827(17)Å, V=3108.0(5)Å3, C29H23F3N2O3PSAg, Mr=675.39, Z=4, Dc=1.443 g/cm3, F(000)=1360, μ=0.816 mm-1, the final R=0.0675 and wR=0.1722 for 3662 observed reflections (I>2σ(I)). Complex 2 crystallizes in triclinic, space group P1 with a=12.9370(11), b=13.5261(13), c=16.4539(15)Å, α=106.7120(10), β=97.3830(10), γ=113.027(2)°, V=2441.2(4)Å3, C94H96F6N4O6P6S2Ag2, Mr=1957.43, Z=1, Dc=1.331 g/cm3, F(000)=1006, μ=0.605 mm-1, the final R=0.0717 and wR=0.1795 for 5128 observed reflections (I>2σ(I)). Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf anion, two N atoms from two 4,4'-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.
2015, 34(1): 147-153
doi: 10.14102/j.cnki.0254-5861.2011-0490
Abstract:
The chelate complex of Cu2+ with 2-hydroxy-(4-methylthio)butanoate (MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA) is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure (C10H18CuO6S2, 1, monoclinic, space group P21/c, Z=2, a=16.158(4), b=4.9733(12), c=9.159(2)Å, β=104.786(4)°) exhibits that two MHA-H ligands coordinate with a CuⅡ ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.
The chelate complex of Cu2+ with 2-hydroxy-(4-methylthio)butanoate (MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA) is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure (C10H18CuO6S2, 1, monoclinic, space group P21/c, Z=2, a=16.158(4), b=4.9733(12), c=9.159(2)Å, β=104.786(4)°) exhibits that two MHA-H ligands coordinate with a CuⅡ ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.
2015, 34(1): 154-160
doi: 10.14102/j.cnki.0254-5861.2011-0391
Abstract:
A novel mixed-ligand coordination polymer [Pb(phen)(NNDS)(H2O)]n·nH2O (1) was obtained from the reaction of 1,10-phenanthroine (phen), Pb(OAc)2 and sodium 1-nitroso-2-naphthol-3,6-disulfonate (Na2NNDS) in a mixed solvent. The complex was characterized by elemental analysis, IR and X-ray single-crystal diffraction. Crystal data for 1: monoclinic, space group P21/c, a=11.5835(9), b=14.6334(11), c=13.9030(11)Å, β=98.4180(10)°, V=2331.3(3)Å3, Z=4, Mr=754.70, Dc=2.150 mg/m3, μ=7.483 mm-1, F(000)=1456, the final R=0.0430 and wR=0.0841 for 4221 observed reflections with I>2σ(I). The Pb(Ⅱ) center is coordinated by six O and two N atoms showing a distorted dodecahedron configuration. The multidentate ligand of NNDS dianion exhibits peculiar coordination mode, and the two O atoms of two sulfonate anions bridge two Pb(Ⅱ) cations into a dimer, and the O atom of nitroso group links the other dimer into 2D sheets extending in the [011] plane. There exist significant π-π stacking interactions between adjacent phen and NNDS. The 3D network is formed by 2D sheets interlinked by hydrogen bonds and π-π stacking interactions. The thermostability of 1 was investigated by TG and DSC.
A novel mixed-ligand coordination polymer [Pb(phen)(NNDS)(H2O)]n·nH2O (1) was obtained from the reaction of 1,10-phenanthroine (phen), Pb(OAc)2 and sodium 1-nitroso-2-naphthol-3,6-disulfonate (Na2NNDS) in a mixed solvent. The complex was characterized by elemental analysis, IR and X-ray single-crystal diffraction. Crystal data for 1: monoclinic, space group P21/c, a=11.5835(9), b=14.6334(11), c=13.9030(11)Å, β=98.4180(10)°, V=2331.3(3)Å3, Z=4, Mr=754.70, Dc=2.150 mg/m3, μ=7.483 mm-1, F(000)=1456, the final R=0.0430 and wR=0.0841 for 4221 observed reflections with I>2σ(I). The Pb(Ⅱ) center is coordinated by six O and two N atoms showing a distorted dodecahedron configuration. The multidentate ligand of NNDS dianion exhibits peculiar coordination mode, and the two O atoms of two sulfonate anions bridge two Pb(Ⅱ) cations into a dimer, and the O atom of nitroso group links the other dimer into 2D sheets extending in the [011] plane. There exist significant π-π stacking interactions between adjacent phen and NNDS. The 3D network is formed by 2D sheets interlinked by hydrogen bonds and π-π stacking interactions. The thermostability of 1 was investigated by TG and DSC.
