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2014 Volume 33 Issue 12
2D/3D-QSAR Studies of [1,2,4]Triazolo[1,5-a]pridinylpyridine Derivatives as Potent Anticancer Agents
2014, 33(12): 1729-1740
doi: 10.14102/j.cnki.0254-5861.2011-0365
Abstract:
By using a combined method of density functional theory (DFT), molecular mechanics (MM2) and statistics for two-dimensional (2D), as well as the comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) methods for three-dimensional (3D), theoretical studies on 2D/3D quantitative structure-activity relationships (QSAR) of 22 novel compounds of [1,2,4]triazolo[1,5-a] pyridinylpyridines acting as PI3K inhibitors against the human colon carcinoma cell line (HCT-116) have been performed. Both the 2D- and 3D-QSAR models established from the random 18 compounds in training set show significant statistical quality and satisfactory predictive ability (R2=0.821, q2=0.773 for 2D-QSAR, R2=0.966, q2=0.668 for CoMFA, R2=0.979, q2=0.753 for CoMSIA). The combined 2D- and 3D-QSAR studies suggest that the moderate-size, hydrophilic and electron-withdrawing group at R1 position, the bulky and hydrophobic group at R2 position, and the minor, hydrophobic, H-bond donor and electron-donating group at R3 position would enhance the anticancer activities. These obtained results help to insight into the action mechanism, and will serve as a basis for the design of new potent anticancer agents.
By using a combined method of density functional theory (DFT), molecular mechanics (MM2) and statistics for two-dimensional (2D), as well as the comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) methods for three-dimensional (3D), theoretical studies on 2D/3D quantitative structure-activity relationships (QSAR) of 22 novel compounds of [1,2,4]triazolo[1,5-a] pyridinylpyridines acting as PI3K inhibitors against the human colon carcinoma cell line (HCT-116) have been performed. Both the 2D- and 3D-QSAR models established from the random 18 compounds in training set show significant statistical quality and satisfactory predictive ability (R2=0.821, q2=0.773 for 2D-QSAR, R2=0.966, q2=0.668 for CoMFA, R2=0.979, q2=0.753 for CoMSIA). The combined 2D- and 3D-QSAR studies suggest that the moderate-size, hydrophilic and electron-withdrawing group at R1 position, the bulky and hydrophobic group at R2 position, and the minor, hydrophobic, H-bond donor and electron-donating group at R3 position would enhance the anticancer activities. These obtained results help to insight into the action mechanism, and will serve as a basis for the design of new potent anticancer agents.
2014, 33(12): 1741-1748
doi: 10.14102/j.cnki.0254-5861.2011-0395
Abstract:
A database of 38 tripeptides with C-terminal proline was constructed to study QSAR of ACE inhibitory peptides. The model was established using PLS based on the three z-scores of 20 coded amino acids. The prediction ability of tripeptides model was improved with proline as terminal. The coefficient of determination (R2) and the cross validated coefficient (QLOO2) of the model are 0.856 and 0.782 respectively. According to the model, two potential ACE inhibitory tripeptides ⅡP and IVP were synthesized. Their IC50 (inhibitor concentration that reduced enzyme activity by 50%) were proved to be 1.58 and 1.39 μM respectively by direct spectrophotometric measurement, and they are very close to the predicted value by the model.
A database of 38 tripeptides with C-terminal proline was constructed to study QSAR of ACE inhibitory peptides. The model was established using PLS based on the three z-scores of 20 coded amino acids. The prediction ability of tripeptides model was improved with proline as terminal. The coefficient of determination (R2) and the cross validated coefficient (QLOO2) of the model are 0.856 and 0.782 respectively. According to the model, two potential ACE inhibitory tripeptides ⅡP and IVP were synthesized. Their IC50 (inhibitor concentration that reduced enzyme activity by 50%) were proved to be 1.58 and 1.39 μM respectively by direct spectrophotometric measurement, and they are very close to the predicted value by the model.
2014, 33(12): 1749-1756
doi: 10.14102/j.cnki.0254-5861.2011-0266
Abstract:
One-pot three component reaction was used to synthesize 1,4,5-trisubstituted 1,2,3-triazole (A) from the corresponding acid chloride, benzyl azide and 1-copper(Ⅰ) phenylethyne. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the orthorhombic space group Pbca, a=14.9815(14), b=9.6496(10), c=25.528(2)Å, Z=8. Furthermore, crystal packing demonstrated a molecular wall-like structure based on supramolecular chains of A, stabilized by CH…O, CH…Br, N…C and CH…π interactions. Molecular geometry in the ground state has been determined by density functional theory (DFT) by B3LYP/6-311G* basis set and compared with the experimental data. The computed vibrational frequencies are compared with the experimental FT-IR data and frontier molecular orbital analyses were performed at the same level of theory. Theoretical parameters are in good agreement with the corresponding X-ray diffraction values.
One-pot three component reaction was used to synthesize 1,4,5-trisubstituted 1,2,3-triazole (A) from the corresponding acid chloride, benzyl azide and 1-copper(Ⅰ) phenylethyne. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the orthorhombic space group Pbca, a=14.9815(14), b=9.6496(10), c=25.528(2)Å, Z=8. Furthermore, crystal packing demonstrated a molecular wall-like structure based on supramolecular chains of A, stabilized by CH…O, CH…Br, N…C and CH…π interactions. Molecular geometry in the ground state has been determined by density functional theory (DFT) by B3LYP/6-311G* basis set and compared with the experimental data. The computed vibrational frequencies are compared with the experimental FT-IR data and frontier molecular orbital analyses were performed at the same level of theory. Theoretical parameters are in good agreement with the corresponding X-ray diffraction values.
2014, 33(12): 1757-1767
doi: 10.14102/j.cnki.0254-5861.2010-1628
Abstract:
The effects of substituent type and position on the proton transfer reaction of 3-hydroxytropolone (3-OHTRN) have been investigated theoretically by using density functional theory at the level of B3LYP/6-31+G** method. The influence of solvent on the proton transfer reactions of substituted 3-OHTRN has been examined using the self-consistent isodensity polarized continuum model (SCI-PCM) in water. As a result, while the proton transfer reaction is kinetically the easiest by substitution on position 3 of -NH2 group in the gas phase, it is kinetically the easiest by substitution on position 5 of the same group in water. In addition, these reactions are either kinetically or thermodynamically easier in the gas phase than that in water, except the reaction of structure with -NH2 group at position 6.
The effects of substituent type and position on the proton transfer reaction of 3-hydroxytropolone (3-OHTRN) have been investigated theoretically by using density functional theory at the level of B3LYP/6-31+G** method. The influence of solvent on the proton transfer reactions of substituted 3-OHTRN has been examined using the self-consistent isodensity polarized continuum model (SCI-PCM) in water. As a result, while the proton transfer reaction is kinetically the easiest by substitution on position 3 of -NH2 group in the gas phase, it is kinetically the easiest by substitution on position 5 of the same group in water. In addition, these reactions are either kinetically or thermodynamically easier in the gas phase than that in water, except the reaction of structure with -NH2 group at position 6.
2014, 33(12): 1768-1772
doi: 10.14102/j.cnki.0254-5861.2011-0342
Abstract:
A new complex, {Bi(Ⅲ)[S2CN(CH2C6H5)2]3}2·2CH3CN, was synthesized and characterized by elemental analysis, IR, TG, 1H NMR and X-ray single-crystal diffraction. The complex crystallizes in the triclinic system, space group P1, with a=12.705(6), b=13.430(6), c=15.489(12)Å, α=102.135(12), β=99.649(12), γ=111.521(9)°, Z=1, V=2315(2)Å3, Dc=1.531 g·cm-3, F(000)=1068, μ=4.116 mm-1, the final R=0.0559, wR=0.1069 and S=1.056. The coordinated geometry of Bi(Ⅲ) with six sulfur atoms from three ligands is a distorted pentagonal pyramidal configuration, and the structural system is formed by weak interactions of Bi…S between two molecules. The complex was valued for its antibacterial activity by agar-streak method. It was found that the complex is weakly active against three of the five tested bacterial organisms.
A new complex, {Bi(Ⅲ)[S2CN(CH2C6H5)2]3}2·2CH3CN, was synthesized and characterized by elemental analysis, IR, TG, 1H NMR and X-ray single-crystal diffraction. The complex crystallizes in the triclinic system, space group P1, with a=12.705(6), b=13.430(6), c=15.489(12)Å, α=102.135(12), β=99.649(12), γ=111.521(9)°, Z=1, V=2315(2)Å3, Dc=1.531 g·cm-3, F(000)=1068, μ=4.116 mm-1, the final R=0.0559, wR=0.1069 and S=1.056. The coordinated geometry of Bi(Ⅲ) with six sulfur atoms from three ligands is a distorted pentagonal pyramidal configuration, and the structural system is formed by weak interactions of Bi…S between two molecules. The complex was valued for its antibacterial activity by agar-streak method. It was found that the complex is weakly active against three of the five tested bacterial organisms.
2014, 33(12): 1773-1778
doi: 10.14102/j.cnki.0254-5861.2011-0369
Abstract:
The NAN-190 analogue 2-(2-(2-(4-(2-methoxyphenyl)piperazin-1-yl)ethoxy)ethyl)isoindoline-1,3-dione (1, C23H27N3O4, Mr=409.48) was synthesized via a three-step reaction and characterized by 1H NMR, 13C NMR, ESIMS and single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pna21 with a=7.6445(15), b=38.851(8), c=7.1316(14)Å, V=2118.0(7)Å3, Z=4, Dc=1.2840 mg/mm3, μ=0.089 mm-1, F(000)=872.4, R=0.0545 and wR=0.1681. The single-crystal X-ray structural analysis reveals that the piperazine ring in compound 1 presents a stable and minimum energy chair conformation. In addition, the preliminary cytotoxic assay shows that the title compound exhibits strong and selective inhibitory activity against DU145 cells (IC50=5.88±1.02 μM).
The NAN-190 analogue 2-(2-(2-(4-(2-methoxyphenyl)piperazin-1-yl)ethoxy)ethyl)isoindoline-1,3-dione (1, C23H27N3O4, Mr=409.48) was synthesized via a three-step reaction and characterized by 1H NMR, 13C NMR, ESIMS and single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pna21 with a=7.6445(15), b=38.851(8), c=7.1316(14)Å, V=2118.0(7)Å3, Z=4, Dc=1.2840 mg/mm3, μ=0.089 mm-1, F(000)=872.4, R=0.0545 and wR=0.1681. The single-crystal X-ray structural analysis reveals that the piperazine ring in compound 1 presents a stable and minimum energy chair conformation. In addition, the preliminary cytotoxic assay shows that the title compound exhibits strong and selective inhibitory activity against DU145 cells (IC50=5.88±1.02 μM).
2014, 33(12): 1779-1783
doi: 10.14102/j.cnki.0254-5861.2011-0380
Abstract:
The title compound 2-(((6-chloropyridin-3-yl)methyl)thio)-5-(pyridin-4-yl)-1,3,4-thiadiazole 5 (C26H18Cl2N8S4) was synthesized, and its structure was confirmed by 1H NMR, MS and elemental analyses and X-ray diffraction. It crystallizes in the triclinic system, space group P1, with a=9.452(4), b=12.335(4), c=13.017(5)Å, α=90.624(5), β=110.541(5), γ=104.879(4)°, Dc=1.561 g/cm3, Z=2, V=1364.9(9)Å3, F(000)=656, the final R=0.0300 and wR=0.0635 for 4206 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 activities to be 9.82%, 44.44% and 20.00%, respectively.
The title compound 2-(((6-chloropyridin-3-yl)methyl)thio)-5-(pyridin-4-yl)-1,3,4-thiadiazole 5 (C26H18Cl2N8S4) was synthesized, and its structure was confirmed by 1H NMR, MS and elemental analyses and X-ray diffraction. It crystallizes in the triclinic system, space group P1, with a=9.452(4), b=12.335(4), c=13.017(5)Å, α=90.624(5), β=110.541(5), γ=104.879(4)°, Dc=1.561 g/cm3, Z=2, V=1364.9(9)Å3, F(000)=656, the final R=0.0300 and wR=0.0635 for 4206 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 activities to be 9.82%, 44.44% and 20.00%, respectively.
2014, 33(12): 1784-1788
doi: 10.14102/j.cnki.0254-5861.2011-0364
Abstract:
The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline (C16H15N3O2, Mr=281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13C NMR, IR, H RMS (ESI) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group I2/c with a=15.0212(10), b=9.4911(6), c=20.3075(13)Å, β=100.776(7)°, V=2844.1(3)Å3, Z=8, Dc=1.314 g/cm3, F(000)=1184.0, μ=0.089 mm-1, the final R=0.0574 and wR=0.1688 for 1701 observed reflections (I>2σ(I)). X-ray analysis indicates three major N(2)-H(2)…O(2), C(13)-H(13)…O(2), N(2)-H(2)…N(3) hydrogen bonds and π-π stacking interactions in the crystal structure. The preliminary biological test shows that the title compound has a good antitumor activity against A549 in vitro with the IC50 value of 35 μmol/L.
The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline (C16H15N3O2, Mr=281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13C NMR, IR, H RMS (ESI) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group I2/c with a=15.0212(10), b=9.4911(6), c=20.3075(13)Å, β=100.776(7)°, V=2844.1(3)Å3, Z=8, Dc=1.314 g/cm3, F(000)=1184.0, μ=0.089 mm-1, the final R=0.0574 and wR=0.1688 for 1701 observed reflections (I>2σ(I)). X-ray analysis indicates three major N(2)-H(2)…O(2), C(13)-H(13)…O(2), N(2)-H(2)…N(3) hydrogen bonds and π-π stacking interactions in the crystal structure. The preliminary biological test shows that the title compound has a good antitumor activity against A549 in vitro with the IC50 value of 35 μmol/L.
2014, 33(12): 1789-1795
doi: 10.14102/j.cnki.0254-5861.2011-0478
Abstract:
Two novel 2-trifluoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-amine derivatives were synthesized by nucleophilic substitution of two appropriate amines with 4-chloro-2-(trifluoromethyl)-5,6,7,8-tetrahydrobenzothieno[2,3-d]pyrimidine, which started from 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile, trifluoroacetic acid (TFA) and phosphorous oxychloride by one-pot procedure. Their structures were determined by single-crystal X-ray diffraction. Compound 1, N-(furan-2-ylmethyl)-2-trifluoromethyl-5,6,7,8-tetrahydrobenzothieno[2,3-d]pyrimidin-4-amine, crystallizes in the monoclinic system, space group C2/c with a=26.352(3), b=7.5991(8), c=17.1423(18)Å, β=114.667(2)°, V=3119.5(6)Å3 and Z=8. Compound 2, N-(3-silatranylpropyl)-2-trifluoromethyl-5,6,7,8-tetrahydrobenzothieno[2,3-d]pyrimidin-4-amine, crystallizes in the monoclinic system, space group P21/n with a=13.4394(13), b=8.9446(9), c=18.9657(18)Å, β=101.9640(10)°, V=2230.3(4)Å3 and Z=4. The preliminary bioassay indicated that compound 2 exhibits more potent antitumor activity against BCG-823 than 5-fluorouracil (5-FU).
Two novel 2-trifluoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-amine derivatives were synthesized by nucleophilic substitution of two appropriate amines with 4-chloro-2-(trifluoromethyl)-5,6,7,8-tetrahydrobenzothieno[2,3-d]pyrimidine, which started from 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile, trifluoroacetic acid (TFA) and phosphorous oxychloride by one-pot procedure. Their structures were determined by single-crystal X-ray diffraction. Compound 1, N-(furan-2-ylmethyl)-2-trifluoromethyl-5,6,7,8-tetrahydrobenzothieno[2,3-d]pyrimidin-4-amine, crystallizes in the monoclinic system, space group C2/c with a=26.352(3), b=7.5991(8), c=17.1423(18)Å, β=114.667(2)°, V=3119.5(6)Å3 and Z=8. Compound 2, N-(3-silatranylpropyl)-2-trifluoromethyl-5,6,7,8-tetrahydrobenzothieno[2,3-d]pyrimidin-4-amine, crystallizes in the monoclinic system, space group P21/n with a=13.4394(13), b=8.9446(9), c=18.9657(18)Å, β=101.9640(10)°, V=2230.3(4)Å3 and Z=4. The preliminary bioassay indicated that compound 2 exhibits more potent antitumor activity against BCG-823 than 5-fluorouracil (5-FU).
2014, 33(12): 1796-1800
doi: 10.14102/j.cnki.0254-5861.2011-0361
Abstract:
A new 1D Cd(Ⅱ) coordination polymer, [Cd(H2biim)2(SO4)]n·3nH2O (1, H2biim=2,2'-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a=6.8405(14), b=17.792(4), c=14.987(3)Å, β=92.68(3), V=1822.1(6)Å3, Z=4, C12H18CdN8O7S, Mr=530.80, Dc=1.935 g/cm3, F(000)=1064, μ(MoKa)=1.371 mm-1, R=0.0280 and wR=0.0617. In 1, adjacent Cd(Ⅱ) atoms are bridged by sulfate anions in bidentate modes to yield a 1D chain. H2biim ligands are located on both sides of the chain in chelating bidentate modes. Further, the H2biim ligands from neighboring chains are paired through π-π interactions to generate a supramolecular layer, which is stabilized by the complicated N-H…O and O-H…O hydrogen bonds. In addition, thermal behavior and luminescent property of 1 have been investigated.
A new 1D Cd(Ⅱ) coordination polymer, [Cd(H2biim)2(SO4)]n·3nH2O (1, H2biim=2,2'-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a=6.8405(14), b=17.792(4), c=14.987(3)Å, β=92.68(3), V=1822.1(6)Å3, Z=4, C12H18CdN8O7S, Mr=530.80, Dc=1.935 g/cm3, F(000)=1064, μ(MoKa)=1.371 mm-1, R=0.0280 and wR=0.0617. In 1, adjacent Cd(Ⅱ) atoms are bridged by sulfate anions in bidentate modes to yield a 1D chain. H2biim ligands are located on both sides of the chain in chelating bidentate modes. Further, the H2biim ligands from neighboring chains are paired through π-π interactions to generate a supramolecular layer, which is stabilized by the complicated N-H…O and O-H…O hydrogen bonds. In addition, thermal behavior and luminescent property of 1 have been investigated.
2014, 33(12): 1801-1806
doi: 10.14102/j.cnki.0254-5861.2011-0286
Abstract:
The 1-azido-2-chloro-4-nitrobenzene was prepared by nucleophilic substitution between 2-chloro-4-nitro-1-(trifluoromethylsulfinyl)benzene and sodium azide, and its structure was characterized by NMR spectrum and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n, Z=8 and Mr=198.57. A cultivation process of the single crystal of unstable aryl azide was provided. The group of trifluoromethyl sulfinyl was found for the first time to be a new excellent leaving group of aromatic nucleophilic substitution reactions.
The 1-azido-2-chloro-4-nitrobenzene was prepared by nucleophilic substitution between 2-chloro-4-nitro-1-(trifluoromethylsulfinyl)benzene and sodium azide, and its structure was characterized by NMR spectrum and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n, Z=8 and Mr=198.57. A cultivation process of the single crystal of unstable aryl azide was provided. The group of trifluoromethyl sulfinyl was found for the first time to be a new excellent leaving group of aromatic nucleophilic substitution reactions.
2014, 33(12): 1807-1812
doi: 10.14102/j.cnki.0254-5861.2011-0359
Abstract:
A novel 2D Cu coordination polymer [Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O]n (2, H2pca=pyrazole-3-carboxylic acid) has been prepared by dissolving a dinuclear Cu complex Cu2(py)3(pca)2(H2O)·(H2O) (1) in DMSO solution and structurally characterized by X-ray diffraction. The polymer crystallizes in space group P1, with a=9.538(3), b=9.714(3), c=10.765(3)Å, α=86.492(6), β=84.007(7), γ=82.592(6)°, Mr=1079.04, V=982.4(5)Å3, Z=1, Dc=1.824 g/cm3, μ=2.425 mm-1 and F(000)=548. The final refinement gave R=0.0785 and wR=0.1940 for 2787 reflections with I>2σ(I). The structure of 2 consists of Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O units, which can be viewed as two dinuclear subunits of Cu2(pca)2(H2O)2 and Cu2(pca)2(DMSO)2 connected to each other alternately, with solvent DMSO and H2O molecules around. The framework features a grid-like topology, with the walls of the grids composed of Cu4(pca)4 units, and the coordinated solvent molecules trapped in the grids.
A novel 2D Cu coordination polymer [Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O]n (2, H2pca=pyrazole-3-carboxylic acid) has been prepared by dissolving a dinuclear Cu complex Cu2(py)3(pca)2(H2O)·(H2O) (1) in DMSO solution and structurally characterized by X-ray diffraction. The polymer crystallizes in space group P1, with a=9.538(3), b=9.714(3), c=10.765(3)Å, α=86.492(6), β=84.007(7), γ=82.592(6)°, Mr=1079.04, V=982.4(5)Å3, Z=1, Dc=1.824 g/cm3, μ=2.425 mm-1 and F(000)=548. The final refinement gave R=0.0785 and wR=0.1940 for 2787 reflections with I>2σ(I). The structure of 2 consists of Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O units, which can be viewed as two dinuclear subunits of Cu2(pca)2(H2O)2 and Cu2(pca)2(DMSO)2 connected to each other alternately, with solvent DMSO and H2O molecules around. The framework features a grid-like topology, with the walls of the grids composed of Cu4(pca)4 units, and the coordinated solvent molecules trapped in the grids.
2014, 33(12): 1813-1818
doi: 10.14102/j.cnki.0254-5861.2011-0389
Abstract:
Two azopyrrole compounds, 1 and 2, have been synthesized and characterized. The crystal of compound 1 is of triclinic, space group P1, with a=6.5632(10), b=7.0805(10), c=17.436(3)Å, α=89.504(2), β=79.460(2), γ=84.2788(2)°, V=792.6(2)Å3, Z=2, C18H21N5, Mr=307.40, Dc=1.288 g/cm, F(000)=328 and μ(MoKα)=0.080 mm-1. The crystal of compound 2 is of triclinic, space group P1, with a=9.7324(8), b=9.9779(8), c=12.3817(11)Å, α=87.052(2), β=71.766(2), γ=70.968(2)°, V=1077.86(16)Å3, Z=2, C23N24H8, Mr=412.5, Dc=1.271 g/cm, F(000)=436 and μ(MoKα)=0.081 mm-1. The molecules of compounds 1 and 2 prefer to form dimers through pairs of N-H…N hydrogen bonds between pyrrole NH groups and pyridine N atoms. In addition, in the crystal of compound 2, the dimers self-assemble into a layer structure through N-H…N hydrogen bonds between pyrrole NH groups and azo N atoms as well as C-H…N hydrogen bonds between the ethyl groups and pyridine N atoms.
Two azopyrrole compounds, 1 and 2, have been synthesized and characterized. The crystal of compound 1 is of triclinic, space group P1, with a=6.5632(10), b=7.0805(10), c=17.436(3)Å, α=89.504(2), β=79.460(2), γ=84.2788(2)°, V=792.6(2)Å3, Z=2, C18H21N5, Mr=307.40, Dc=1.288 g/cm, F(000)=328 and μ(MoKα)=0.080 mm-1. The crystal of compound 2 is of triclinic, space group P1, with a=9.7324(8), b=9.9779(8), c=12.3817(11)Å, α=87.052(2), β=71.766(2), γ=70.968(2)°, V=1077.86(16)Å3, Z=2, C23N24H8, Mr=412.5, Dc=1.271 g/cm, F(000)=436 and μ(MoKα)=0.081 mm-1. The molecules of compounds 1 and 2 prefer to form dimers through pairs of N-H…N hydrogen bonds between pyrrole NH groups and pyridine N atoms. In addition, in the crystal of compound 2, the dimers self-assemble into a layer structure through N-H…N hydrogen bonds between pyrrole NH groups and azo N atoms as well as C-H…N hydrogen bonds between the ethyl groups and pyridine N atoms.
2014, 33(12): 1819-1825
doi: 10.14102/j.cnki.0254-5861.2011-0377
Abstract:
A new Ni(Ⅱ) coordination polymer [Ni(L)2(SCN)2]n (L=1,4-bis(benzimidazol-1-yl)butane) was synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group C2/c with a=9.4760(3), b=24.0408(8), c=16.5871(5)Å, β=99.832(3)°, V=3723.2(2)Å3, Z=4, Dc=1.348 g/cm3, F(000)=1576, the final R=0.0486 and wR=0.0936 for 2938 observed reflections with I>2σ(I) for the complex. Structural analysis shows that the coordination polymer possesses a 2D (4,4) layer structure which is composed of Ni(Ⅱ) centers bridged by L ligand with two kinds of conformations and further assembled into a 3D supramolecular network via π-π stacking interactions. In addition, the fluorescence and catalytic properties, for the degradation of Congo red, of the complex were investigated.
A new Ni(Ⅱ) coordination polymer [Ni(L)2(SCN)2]n (L=1,4-bis(benzimidazol-1-yl)butane) was synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group C2/c with a=9.4760(3), b=24.0408(8), c=16.5871(5)Å, β=99.832(3)°, V=3723.2(2)Å3, Z=4, Dc=1.348 g/cm3, F(000)=1576, the final R=0.0486 and wR=0.0936 for 2938 observed reflections with I>2σ(I) for the complex. Structural analysis shows that the coordination polymer possesses a 2D (4,4) layer structure which is composed of Ni(Ⅱ) centers bridged by L ligand with two kinds of conformations and further assembled into a 3D supramolecular network via π-π stacking interactions. In addition, the fluorescence and catalytic properties, for the degradation of Congo red, of the complex were investigated.
2014, 33(12): 1826-1830
doi: 10.14102/j.cnki.0254-5861.2011-0378
Abstract:
A new coordination complex [Cd(pda)(pyz)(H2O)2]n (1, H2pda=1,4-phenylenediacetic acid, pyz=pyrazine) have been synthesized and structurally characterized. Crystal data for the title complex are as follows: orthorhombic system, space group Ccmb with a=11.5245(3) b=19.5069(5) c=11.4231(3)Ǻ, V=2568.00(12)Ǻ3, Mr=188.31, Z=16, F(000)=1480, Dc=1.948 g/cm3, μ(MoKα)=1.725 mm-1, R=0.0195 and wR=0.0462 for 1357 observed reflections with I>2σ(I). In the title complex, the central Cd(Ⅱ) ion is located in a distorted octahedral coordination environment. Two Cd(Ⅱ) ions are bridged by two pda2- ligands and one pyz ligand to form a bi-loop structure. Luminescent property of the complex has also been studied.
A new coordination complex [Cd(pda)(pyz)(H2O)2]n (1, H2pda=1,4-phenylenediacetic acid, pyz=pyrazine) have been synthesized and structurally characterized. Crystal data for the title complex are as follows: orthorhombic system, space group Ccmb with a=11.5245(3) b=19.5069(5) c=11.4231(3)Ǻ, V=2568.00(12)Ǻ3, Mr=188.31, Z=16, F(000)=1480, Dc=1.948 g/cm3, μ(MoKα)=1.725 mm-1, R=0.0195 and wR=0.0462 for 1357 observed reflections with I>2σ(I). In the title complex, the central Cd(Ⅱ) ion is located in a distorted octahedral coordination environment. Two Cd(Ⅱ) ions are bridged by two pda2- ligands and one pyz ligand to form a bi-loop structure. Luminescent property of the complex has also been studied.
A 3-Connected 3D Microporous Metal-organic Framework with Intersected Channels and Rare DEH Topology
2014, 33(12): 1831-1835
doi: 10.14102/j.cnki.0254-5861.2011-0387
Abstract:
A novel metal-organic coordination polymer {[Cd(mppdc)(H2O)]·H2O}n (1, H2mppdc=2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylic acid) was synthesized from the reaction of H2mppdc, Cd(NO3)2·4H2O and CH3OH under solvothermal conditions. The crystal is of tetragonal system, space group I41/a, with a=19.109(2), b=19.109(2), c=24.317(7)Å, V=8880(3)Å3, Z=16, Mr=417.68, Dc=1.250 Mg/m3, F(000)=3328, the final R=0.0516 and wR=0.1185 (I>2σ(I)). Complex 1 displays a 3D microporous metal-organic framework with intersected channels and rare (8210) DEH topology. The complex exhibits strong photoluminescence at room temperature in the solid state.
A novel metal-organic coordination polymer {[Cd(mppdc)(H2O)]·H2O}n (1, H2mppdc=2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylic acid) was synthesized from the reaction of H2mppdc, Cd(NO3)2·4H2O and CH3OH under solvothermal conditions. The crystal is of tetragonal system, space group I41/a, with a=19.109(2), b=19.109(2), c=24.317(7)Å, V=8880(3)Å3, Z=16, Mr=417.68, Dc=1.250 Mg/m3, F(000)=3328, the final R=0.0516 and wR=0.1185 (I>2σ(I)). Complex 1 displays a 3D microporous metal-organic framework with intersected channels and rare (8210) DEH topology. The complex exhibits strong photoluminescence at room temperature in the solid state.
2014, 33(12): 1836-1842
doi: 10.14102/j.cnki.0254-5861.2011-0319
Abstract:
A new coordination polymer, [Mn(3,4-pybz)2]n·3(H2O) (1), has been hydrothermally synthesized from MnCl2·4H2O and an unsymmetrical 3-pyridin-4-yl-benzoic acid (3,4-Hpybz), and characterized by IR, elemental analysis, thermogravimetric analysis, and singlecrystal X-ray diffraction. In complex 1, each 3,4-pybz ligand represents a three-connected node to combine with the six-connected Mn(Ⅱ) ions, generating a 3D binodal (3,6)-connected ant network. In addition, magnetic investigations reveal that complex 1 exhibits an antiferromagnetic behavior. According to the crystal structure, the full-geometrical optimization of complex 1 was carried out by using hybrid DFT methods at the B3LYP/6-31G(d) level. Meantime, the DFT-BS approach was applied to study the magnetic coupling behavior for complex 1, and the result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.
A new coordination polymer, [Mn(3,4-pybz)2]n·3(H2O) (1), has been hydrothermally synthesized from MnCl2·4H2O and an unsymmetrical 3-pyridin-4-yl-benzoic acid (3,4-Hpybz), and characterized by IR, elemental analysis, thermogravimetric analysis, and singlecrystal X-ray diffraction. In complex 1, each 3,4-pybz ligand represents a three-connected node to combine with the six-connected Mn(Ⅱ) ions, generating a 3D binodal (3,6)-connected ant network. In addition, magnetic investigations reveal that complex 1 exhibits an antiferromagnetic behavior. According to the crystal structure, the full-geometrical optimization of complex 1 was carried out by using hybrid DFT methods at the B3LYP/6-31G(d) level. Meantime, the DFT-BS approach was applied to study the magnetic coupling behavior for complex 1, and the result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.
2014, 33(12): 1843-1848
doi: 10.14102/j.cnki.0254-5861.2011-0417
Abstract:
A new 3D Cd(Ⅱ) coordination polymer, [Cd(Hpidc)]n (1, H3pidc=2-(pyrid-2-yl)-1H-imidazole-4,5-dicarboxy acid), has been prepared and characterized by elemental analysis, IR spectra, PXRD, and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group Fdd2 with a=22.833(9), b=25.536(9), c=7.437(3)Å, V=4336(3)Å3, Z=16, Dc=2.105 Mg·m-3, μ=2.025 mm-1, F(000)=2656, and the final R=0.0261 and wR=0.0636. The structure determination reveals that 1 exhibits a rare 3D 3-connected lig net with a point symbol of (82·10). In addition, the solid state properties such as thermogravimetric analysis and luminescence of 1 were also studied.
A new 3D Cd(Ⅱ) coordination polymer, [Cd(Hpidc)]n (1, H3pidc=2-(pyrid-2-yl)-1H-imidazole-4,5-dicarboxy acid), has been prepared and characterized by elemental analysis, IR spectra, PXRD, and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group Fdd2 with a=22.833(9), b=25.536(9), c=7.437(3)Å, V=4336(3)Å3, Z=16, Dc=2.105 Mg·m-3, μ=2.025 mm-1, F(000)=2656, and the final R=0.0261 and wR=0.0636. The structure determination reveals that 1 exhibits a rare 3D 3-connected lig net with a point symbol of (82·10). In addition, the solid state properties such as thermogravimetric analysis and luminescence of 1 were also studied.
2014, 33(12): 1849-1853
doi: 10.14102/j.cnki.0254-5861.2011-0371
Abstract:
A new cadmium(Ⅱ) complex Cd(OBBA)2(2,2'-bipy)2 with 2-benzoylbenzoic acid (HOBBA) and 2,2-bipyridine (2,2'-bipy) as ligands has been synthesized. Crystal data for the complex are as follows: monoclinic, space group P21/c with a=16.402(3), b=10.4191(18), c=23.395(4)Å, β=91.765(2)°, V=3996.2(12)Å3, Dc=1.455 g·cm-3, Z=4, μ(MoKα)=0.603 mm-1, F(000)=1784, the final R=0.0218 and wR=0.0558. In the electrode reaction, its electron transfer is quasi reversible and the electrode reaction corresponds to Cd(Ⅱ)/Cd(0). Under 618 nm radiation, the title complex shows a strong fluorescent band at around 326 nm. In addition, in the range of 2~300 K, this complex displays diamagnetic property.
A new cadmium(Ⅱ) complex Cd(OBBA)2(2,2'-bipy)2 with 2-benzoylbenzoic acid (HOBBA) and 2,2-bipyridine (2,2'-bipy) as ligands has been synthesized. Crystal data for the complex are as follows: monoclinic, space group P21/c with a=16.402(3), b=10.4191(18), c=23.395(4)Å, β=91.765(2)°, V=3996.2(12)Å3, Dc=1.455 g·cm-3, Z=4, μ(MoKα)=0.603 mm-1, F(000)=1784, the final R=0.0218 and wR=0.0558. In the electrode reaction, its electron transfer is quasi reversible and the electrode reaction corresponds to Cd(Ⅱ)/Cd(0). Under 618 nm radiation, the title complex shows a strong fluorescent band at around 326 nm. In addition, in the range of 2~300 K, this complex displays diamagnetic property.
2014, 33(12): 1854-1859
doi: 10.14102/j.cnki.0254-5861.2011-0532
Abstract:
A new 3D metal organic framework, {[Zn4(dna)4(dpb)2(H2O)2]·H2O}n(1, H2dna=4,6-dimethyl-5-nitroisophthalic acid; dpb=1,4-bis-(4-pyridyl)-benzene), has been solvothermally synthesized and characterized by TGA, and single-crystal X-ray diffraction. Compound 1 crystalizes in monoclinic, space group P21/c with a=15.169(2), b=13.0539(18), c=9.1669(13)Å, C18H17N2O8Zn, Mr=454.71, V=1798.9(4)Å3, Z=4, Dc=1.679 g·cm-3, μ=1.418 mm-1, F(000)=932, 2.07≤θ≤25.00°, λ(MoKα)=0.71073Å, T=273(2) K, the final R=0.0300, wR=0.0754 and S=1.028. X-ray diffraction analysis reveals that complex 1 possesses a 3D pcu framework constructed by (4,4)-connected 2D layers and dpb linkers. In addition, the solid state luminescent property of complex 1 at room temperature was also investigated.
A new 3D metal organic framework, {[Zn4(dna)4(dpb)2(H2O)2]·H2O}n(1, H2dna=4,6-dimethyl-5-nitroisophthalic acid; dpb=1,4-bis-(4-pyridyl)-benzene), has been solvothermally synthesized and characterized by TGA, and single-crystal X-ray diffraction. Compound 1 crystalizes in monoclinic, space group P21/c with a=15.169(2), b=13.0539(18), c=9.1669(13)Å, C18H17N2O8Zn, Mr=454.71, V=1798.9(4)Å3, Z=4, Dc=1.679 g·cm-3, μ=1.418 mm-1, F(000)=932, 2.07≤θ≤25.00°, λ(MoKα)=0.71073Å, T=273(2) K, the final R=0.0300, wR=0.0754 and S=1.028. X-ray diffraction analysis reveals that complex 1 possesses a 3D pcu framework constructed by (4,4)-connected 2D layers and dpb linkers. In addition, the solid state luminescent property of complex 1 at room temperature was also investigated.
2014, 33(12): 1860-1864
doi: 10.14102/j.cnki.0254-5861.2011-0534
Abstract:
A novel terbium(Ⅲ) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c with a=9.2252(11), b=14.1477(16), c=10.5134(12)Å, β=95.770(2)°, V=1365.2(3)Å3, Z=4, Dc=2.248 g·cm-3, F(000)=880, the final R=0.0176 and wR=0.0411 for 2149 observed reflections with I>2σ(I). The complex is extended into a three-dimensional network structure with 24-atom rings which are composed of Tb, C and O atoms. The complex displays green fluorescence emission in the solid state at room temperature, which corresponds to 5D4→7F5 transition of the Tb(Ⅲ) ion.
A novel terbium(Ⅲ) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c with a=9.2252(11), b=14.1477(16), c=10.5134(12)Å, β=95.770(2)°, V=1365.2(3)Å3, Z=4, Dc=2.248 g·cm-3, F(000)=880, the final R=0.0176 and wR=0.0411 for 2149 observed reflections with I>2σ(I). The complex is extended into a three-dimensional network structure with 24-atom rings which are composed of Tb, C and O atoms. The complex displays green fluorescence emission in the solid state at room temperature, which corresponds to 5D4→7F5 transition of the Tb(Ⅲ) ion.
2014, 33(12): 1865-1874
doi: 10.14102/j.cnki.0254-5861.2011-0549
Abstract:
β-NaYF4:Yb3+,Er3+ microrods with average length of 10 μm and diameter of 2.5 μm were synthesized through hydrothermal method. Based on the obtained microrods, transparent and flexible film with upconversion luminescence property was prepared through inorganic-organic composition method by using co-polymerization product of isobornylmethacrylate and urethane acrylate as the polymer substrate. The prepared film shows excellent optical transmission in the visible region with average transmission of 81.3% at high doping concentration (2 wt%) of β-NaYF4:Yb3+,Er3+ microrods. By directing and moving NIR laser beam toward the prepared film with high scanning speed, visible light is effectively emitted and various images are able to display.
β-NaYF4:Yb3+,Er3+ microrods with average length of 10 μm and diameter of 2.5 μm were synthesized through hydrothermal method. Based on the obtained microrods, transparent and flexible film with upconversion luminescence property was prepared through inorganic-organic composition method by using co-polymerization product of isobornylmethacrylate and urethane acrylate as the polymer substrate. The prepared film shows excellent optical transmission in the visible region with average transmission of 81.3% at high doping concentration (2 wt%) of β-NaYF4:Yb3+,Er3+ microrods. By directing and moving NIR laser beam toward the prepared film with high scanning speed, visible light is effectively emitted and various images are able to display.
2014, 33(12): 1875-1880
doi: 10.14102/j.cnki.0254-5861.2011-0559
Abstract:
β-NaYF4:Yb3+,Er3+ microrods were synthesized through hydrothermal methods. Polyethylene glycol with molecular weight of 6000 was used as surfactant. A series of transparent silica gel films with upconversion luminescence property was prepared through sol-gel method; the prepared β-NaYF4:Yb3+,Er3+ microrods were used as activator. The silica gel films show strong upconversion emission under excitation of 980-nm laser beam.
β-NaYF4:Yb3+,Er3+ microrods were synthesized through hydrothermal methods. Polyethylene glycol with molecular weight of 6000 was used as surfactant. A series of transparent silica gel films with upconversion luminescence property was prepared through sol-gel method; the prepared β-NaYF4:Yb3+,Er3+ microrods were used as activator. The silica gel films show strong upconversion emission under excitation of 980-nm laser beam.
