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2015 Volume 34 Issue 3
2015, 34(3): 319-323
doi: 10.14102/j.cnki.0254-5861.2011-0525
Abstract:
Two novel dihydropyran compounds (1 and 2) containing a triphenylamine group were synthesized and characterized. The structure of compound 2 was verified by single-crystal X-ray crystallography. It crystallizes in triclinic, space group P1 with a=6.9943(4), b=8.1360(4), c=23.9274(14)Å, α=87.692(4), β=88.940(5), γ=85.223(4)°, V=1355.62(13)Å3, Z=2, F(000)=520, Dc=1.199 Mg/m3, Mr=489.24 and μ=0.075 mm-1. The UV-vis absorption and fluorescence of the two compounds were discussed. The two compounds exhibited strong blue emissions under ultraviolet light excitation. The molecular structure and HOMO and LUMO levels of compound 2 were calculated by density functional theory (DFT) at the B3LYP/6-31G(d) level.
Two novel dihydropyran compounds (1 and 2) containing a triphenylamine group were synthesized and characterized. The structure of compound 2 was verified by single-crystal X-ray crystallography. It crystallizes in triclinic, space group P1 with a=6.9943(4), b=8.1360(4), c=23.9274(14)Å, α=87.692(4), β=88.940(5), γ=85.223(4)°, V=1355.62(13)Å3, Z=2, F(000)=520, Dc=1.199 Mg/m3, Mr=489.24 and μ=0.075 mm-1. The UV-vis absorption and fluorescence of the two compounds were discussed. The two compounds exhibited strong blue emissions under ultraviolet light excitation. The molecular structure and HOMO and LUMO levels of compound 2 were calculated by density functional theory (DFT) at the B3LYP/6-31G(d) level.
2015, 34(3): 324-334
doi: 10.14102/j.cnki.0254-5861.2011-0518
Abstract:
Quantitative structure-activity relationship (QSAR) model was developed for predicting the mutagenicity of aromatic compounds. The log revertants data of S. typhimurium TA98 strain from Ames test have been collected. 225 aromatic compounds were randomly divided into the training set with 186 molecules and test set with 39 molecules. Multiple linear regression (MLR) analysis was used to select six descriptors from thousands of descriptors calculated by semiempirical AM1 and E-dragon methods. The final QSAR model with six descriptors was internal and external validated. In addition, to validate the utility of our QSAR model for the chemical evaluation, three aromatic compounds were taken to test the predictive ability and reliability of the model experimentally. The compounds selected for testing were not based on the predictions, thus spanning the range of predicted probabilities. The subsequently generated results of the Ames test were in good correspondence with the predictions and confirmed this approach as a useful means of predicting likely mutagenic risk of aromatic compounds.
Quantitative structure-activity relationship (QSAR) model was developed for predicting the mutagenicity of aromatic compounds. The log revertants data of S. typhimurium TA98 strain from Ames test have been collected. 225 aromatic compounds were randomly divided into the training set with 186 molecules and test set with 39 molecules. Multiple linear regression (MLR) analysis was used to select six descriptors from thousands of descriptors calculated by semiempirical AM1 and E-dragon methods. The final QSAR model with six descriptors was internal and external validated. In addition, to validate the utility of our QSAR model for the chemical evaluation, three aromatic compounds were taken to test the predictive ability and reliability of the model experimentally. The compounds selected for testing were not based on the predictions, thus spanning the range of predicted probabilities. The subsequently generated results of the Ames test were in good correspondence with the predictions and confirmed this approach as a useful means of predicting likely mutagenic risk of aromatic compounds.
2015, 34(3): 335-343
doi: 10.14102/j.cnki.0254-5861.2011-0312
Abstract:
The charge transfer rates of perylene and its four derivatives were studied at the level of B3LYP/6-31G** by density functional theory. The results showed that the perylene and its four derivatives belonged to the semiconductor molecules, which released energy when electron was injected. Therefore, they were suitable to be used as the electron injection material. The introduction of OH group can improve the electron transfer rate significantly. The formations of intramolecular hydrogen bonds were unfavorable to the hole transfer, but conducive to the electron transfer. The perylene derivatives, 2,5-3,4,5-(trifluorophenyl)ethynyl-8,11-3,4,5-trihydroxyphenyl ethynyl, designed in this article had the hole transfer rate of 1.57 cm2/V·s-1. Therefore, this kind of material will be potential hole transfer material with high transfer efficiency.
The charge transfer rates of perylene and its four derivatives were studied at the level of B3LYP/6-31G** by density functional theory. The results showed that the perylene and its four derivatives belonged to the semiconductor molecules, which released energy when electron was injected. Therefore, they were suitable to be used as the electron injection material. The introduction of OH group can improve the electron transfer rate significantly. The formations of intramolecular hydrogen bonds were unfavorable to the hole transfer, but conducive to the electron transfer. The perylene derivatives, 2,5-3,4,5-(trifluorophenyl)ethynyl-8,11-3,4,5-trihydroxyphenyl ethynyl, designed in this article had the hole transfer rate of 1.57 cm2/V·s-1. Therefore, this kind of material will be potential hole transfer material with high transfer efficiency.
2015, 34(3): 344-348
doi: 10.14102/j.cnki.0254-5861.2011-0530
Abstract:
The title compound, 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)thiazol-2-amine, was synthesized via the reduction of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a=7.91944(19), b=10.5250(3), c=24.4985(6)Å, Z=4, V=2041.66(9)Å3, Mr=599.22, Dc=1.949 Mg/m3, S=1.120, μ=3.203 mm-1, F(000)=1152, the final R=0.0283 and wR=0.0592 for 3490 observed reflections (I>2σ(I)). X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O(2)-H(2A)…O(1), O(2)-H(2B)…N(1) and N(5)-H(5)…O(2), and an octatomic ring R11(8) is formed via intramolecular hydrogen bond of O(1)-H(1A)…N(4). Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.
The title compound, 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)thiazol-2-amine, was synthesized via the reduction of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a=7.91944(19), b=10.5250(3), c=24.4985(6)Å, Z=4, V=2041.66(9)Å3, Mr=599.22, Dc=1.949 Mg/m3, S=1.120, μ=3.203 mm-1, F(000)=1152, the final R=0.0283 and wR=0.0592 for 3490 observed reflections (I>2σ(I)). X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O(2)-H(2A)…O(1), O(2)-H(2B)…N(1) and N(5)-H(5)…O(2), and an octatomic ring R11(8) is formed via intramolecular hydrogen bond of O(1)-H(1A)…N(4). Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.
2015, 34(3): 349-358
doi: 10.14102/j.cnki.0254-5861.2011-0520
Abstract:
In this study, ent-Kaurane-3β,16β,17-triol (1) and ent-kaurane-2α,16β,17-triol (2), were isolated from the leaves of Rubus corchorifolius L. f. Their structures were elucidated based on extensive spectroscopic analysis. NMR experiments identified the two compounds and X-ray crystallographic analysis confirmed their crystal structures. The crystal of 1 belongs to monoclinic with space group P21 and a=10.7641(3), b=7.2789(3), c=11.7862(4)Å, β=95.275(3)°, V=919.55(6)Å3, Z=2, C20H34O4, Mr=322.49 g/mol, Dc=1.230 g/m3, F(000)=376, λ=1.54178Å, μ=0.661 mm-1, R=0.0319, and wR=0.0811 for 10889 observed reflections (I>2σ(I)). The crystal of 2 is classified as orthorhombic with space group P212121 and a=10.7641(3), b=12.72224(19), c=21.3929(3)Å, V=1748.94(4)Å3, Z=4, C20H34O4, Mr=322.47, Dc=1.225 Mg/m3 F(000)=712, λ=1.54184Å, μ=0.625 mm-1, R=0.0303 and wR=0.0759 for 10470 observed reflections (I>2σ(I)). Meanwhile, the compound revealed low inhibitory activities toward HepG2, MCF-7, and SCG-7901 cells.
In this study, ent-Kaurane-3β,16β,17-triol (1) and ent-kaurane-2α,16β,17-triol (2), were isolated from the leaves of Rubus corchorifolius L. f. Their structures were elucidated based on extensive spectroscopic analysis. NMR experiments identified the two compounds and X-ray crystallographic analysis confirmed their crystal structures. The crystal of 1 belongs to monoclinic with space group P21 and a=10.7641(3), b=7.2789(3), c=11.7862(4)Å, β=95.275(3)°, V=919.55(6)Å3, Z=2, C20H34O4, Mr=322.49 g/mol, Dc=1.230 g/m3, F(000)=376, λ=1.54178Å, μ=0.661 mm-1, R=0.0319, and wR=0.0811 for 10889 observed reflections (I>2σ(I)). The crystal of 2 is classified as orthorhombic with space group P212121 and a=10.7641(3), b=12.72224(19), c=21.3929(3)Å, V=1748.94(4)Å3, Z=4, C20H34O4, Mr=322.47, Dc=1.225 Mg/m3 F(000)=712, λ=1.54184Å, μ=0.625 mm-1, R=0.0303 and wR=0.0759 for 10470 observed reflections (I>2σ(I)). Meanwhile, the compound revealed low inhibitory activities toward HepG2, MCF-7, and SCG-7901 cells.
2015, 34(3): 359-364
doi: 10.14102/j.cnki.0254-5861.2011-0513
Abstract:
The title compound 2-(3-methyl-5-(methylthio)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione (C12H10N4O2S, Mr=274.30) has been synthesized by a three-step procedure including the cyclization, hydrazinolysis and substitution reactions, and its crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c with a=12.264(3), b=14.646(3), c=14.349(4)Å, β=91.69(3)°, μ=0.255 mm-1, Mr=274.30, V=2576.2(10)Å3, Z=8, Dc=1.414 g/cm3, F(000)=1136, R=0.0487 and wR=0.1329 for 4048 observed reflections with I>2σ(I). In addition, the preliminary bioassay suggested that the title compound 6 exhibits relatively good antitumor activity against HT-29 and MCF-7.
The title compound 2-(3-methyl-5-(methylthio)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione (C12H10N4O2S, Mr=274.30) has been synthesized by a three-step procedure including the cyclization, hydrazinolysis and substitution reactions, and its crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c with a=12.264(3), b=14.646(3), c=14.349(4)Å, β=91.69(3)°, μ=0.255 mm-1, Mr=274.30, V=2576.2(10)Å3, Z=8, Dc=1.414 g/cm3, F(000)=1136, R=0.0487 and wR=0.1329 for 4048 observed reflections with I>2σ(I). In addition, the preliminary bioassay suggested that the title compound 6 exhibits relatively good antitumor activity against HT-29 and MCF-7.
2015, 34(3): 365-372
doi: 10.14102/j.cnki.0254-5861.2011-0503
Abstract:
A novel donor-acceptor (D-A) triphenylamino terpyridine derivative Lwas facilely synthesized and fully characterized, and its single crystals were obtained and determined by X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a=11.760(5), b=12.516(5), c=12.850(5)Å, α=67.141(5), β=65.284(5), γ=75.876(5)°, Mr=621.54, V=1575.6(11)Å3, Z=2, Dc=1.310 g/cm3, μ=0.245 mm-1, F(000)=648, the final R=0.0671 and wR=0.1869 for 11328 observed reflections with I>2σ(I). Linear and nonlinear optical properties of terpyridine derivative Lwere systematically investigated. The maximum two-photon cross-section of Lwas 382.5 GM (Goeppert-Mayer), measured by two-photon excited fluorescence (TPEF) method. This result demonstrates that the increase of intramolecular charge transfer (ICT) leads to enhanced two-photon absorption (2PA), which could be achieved by introducing additional electron-donor groups to the molecular framework.
A novel donor-acceptor (D-A) triphenylamino terpyridine derivative Lwas facilely synthesized and fully characterized, and its single crystals were obtained and determined by X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a=11.760(5), b=12.516(5), c=12.850(5)Å, α=67.141(5), β=65.284(5), γ=75.876(5)°, Mr=621.54, V=1575.6(11)Å3, Z=2, Dc=1.310 g/cm3, μ=0.245 mm-1, F(000)=648, the final R=0.0671 and wR=0.1869 for 11328 observed reflections with I>2σ(I). Linear and nonlinear optical properties of terpyridine derivative Lwere systematically investigated. The maximum two-photon cross-section of Lwas 382.5 GM (Goeppert-Mayer), measured by two-photon excited fluorescence (TPEF) method. This result demonstrates that the increase of intramolecular charge transfer (ICT) leads to enhanced two-photon absorption (2PA), which could be achieved by introducing additional electron-donor groups to the molecular framework.
2015, 34(3): 373-378
doi: 10.14102/j.cnki.0254-5861.2011-0504
Abstract:
The title compound Ph3P=C(H)C(O)PhNO2 (L) has been prepared by the addition of triphenylphosphine in acetone as solvent to 2-bromo-1-(3-nitrophenyl)ethanone followed by the addition of alkaline solution of sodium hydroxide. The yellow crystals of the title ylide were grown in methanol/chloroform solution by drop method without stirring at room temperature. The solid state structure of ylide has been established by X-ray crystallography analysis. In the molecule of the title compound, the geometry around the P atom is nearly tetrahedral and the O atom is in synperiplanar orientation to the P atom. The nitrophenyl ring is twisted with respect to the plane of the carbonyl group through an angle of 36.6(1)°. The crystal (C26H20NO3P, Mr=425.40) belongs to the monoclinic system, space group P21/n with a=10.889(3), b=14.467(3), c=13.872(4)Å, β=103.08(3)°, V=2128.6(10)Å3, Z=4, T=100(2) K, R=0.059 and wR=0.163 for 3984 observed reflections with I>2σ(I).
The title compound Ph3P=C(H)C(O)PhNO2 (L) has been prepared by the addition of triphenylphosphine in acetone as solvent to 2-bromo-1-(3-nitrophenyl)ethanone followed by the addition of alkaline solution of sodium hydroxide. The yellow crystals of the title ylide were grown in methanol/chloroform solution by drop method without stirring at room temperature. The solid state structure of ylide has been established by X-ray crystallography analysis. In the molecule of the title compound, the geometry around the P atom is nearly tetrahedral and the O atom is in synperiplanar orientation to the P atom. The nitrophenyl ring is twisted with respect to the plane of the carbonyl group through an angle of 36.6(1)°. The crystal (C26H20NO3P, Mr=425.40) belongs to the monoclinic system, space group P21/n with a=10.889(3), b=14.467(3), c=13.872(4)Å, β=103.08(3)°, V=2128.6(10)Å3, Z=4, T=100(2) K, R=0.059 and wR=0.163 for 3984 observed reflections with I>2σ(I).
2015, 34(3): 379-385
doi: 10.14102/j.cnki.0254-5861.2011-0509
Abstract:
N-4-(bromobutanoyl)-N'-(o-, m-and p-tolyl)thioureas 3a, 3b and 3c respectively, were synthesized by the reaction of 4-bromobutanoylisothiocyanate with p-, m-and o-toludine. The products were characterized by IR, and NMR spectroscopic techniques. The two carbonoylthiourea isomers N-4-(bromobutanoyl)-N'-(3-methylphenyl)thiourea (3b) and N-4-(bromobutanoyl)-N'-(4-methylphenyl)thiourea (3c) were obtained in crystalline form by recrystallization from DMSO. Xray crystallographic studies showed that both compounds 3b and 3c crystallize in triclinic system with space group of P1. The molecules adopt trans-cis configuration with respect to the positions of 4-bromobutanoyl and tolyl groups respectively, against the thiono C=S bond across their C-N bonds. The configuration is attributed by the intrahydrogen bond between the carbonyl oxygen and amide hydrogen atoms. Both crystal structures are stabilized by N-H…S intermolecular hydrogen bonds to form dimers and arranged along the b axis.
N-4-(bromobutanoyl)-N'-(o-, m-and p-tolyl)thioureas 3a, 3b and 3c respectively, were synthesized by the reaction of 4-bromobutanoylisothiocyanate with p-, m-and o-toludine. The products were characterized by IR, and NMR spectroscopic techniques. The two carbonoylthiourea isomers N-4-(bromobutanoyl)-N'-(3-methylphenyl)thiourea (3b) and N-4-(bromobutanoyl)-N'-(4-methylphenyl)thiourea (3c) were obtained in crystalline form by recrystallization from DMSO. Xray crystallographic studies showed that both compounds 3b and 3c crystallize in triclinic system with space group of P1. The molecules adopt trans-cis configuration with respect to the positions of 4-bromobutanoyl and tolyl groups respectively, against the thiono C=S bond across their C-N bonds. The configuration is attributed by the intrahydrogen bond between the carbonyl oxygen and amide hydrogen atoms. Both crystal structures are stabilized by N-H…S intermolecular hydrogen bonds to form dimers and arranged along the b axis.
2015, 34(3): 386-392
doi: 10.14102/j.cnki.0254-5861.2011-0465
Abstract:
Two complexes, [Cd(nphth)(2,2'-bipy)(H2O)]2·2H2O (1) and [Cd(nphth)(4,4'-bipy)(H2O)]n (2) (nphth=3-nitrophthalate, 2,2'-bipy=2,2'-bipyridine, 4,4'-bipy=4,4'-bipyridine), were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in triclinic with space group P1, a=0.7599(4), b=1.0551(6), c=1.2448(6) nm, α=88.96(2), β=75.40(2), γ=76.76(2)°, V=0.9393(9) nm3, Z=1, Dc=1.816 Mg/m3, F(000)=512, μ=1.217 mm-1, S=0.946, the final R=0.0238 and wR=0.0631. Complex 2 crystallizes in monoclinic, space group P21/c, a=0.737(5), b=2.338(1), c=1.0030(6) nm, β=96.359(9)°, V=1.803(2) nm3, Z=4, Dc=1.826 Mg/m3, F(000)=984, μ=1.260 mm-1, S=1.016, the final R=0.0455 and wR=0.1007. Complex 1 exhibits a discrete cyclic binuclear structure and complex 2 possesses a 2D layer structure with cyclic binuclear unit. The fluorescent spectrum study shows that complex 1 exhibits fluorescent emission in the solid state at room temperature.
Two complexes, [Cd(nphth)(2,2'-bipy)(H2O)]2·2H2O (1) and [Cd(nphth)(4,4'-bipy)(H2O)]n (2) (nphth=3-nitrophthalate, 2,2'-bipy=2,2'-bipyridine, 4,4'-bipy=4,4'-bipyridine), were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in triclinic with space group P1, a=0.7599(4), b=1.0551(6), c=1.2448(6) nm, α=88.96(2), β=75.40(2), γ=76.76(2)°, V=0.9393(9) nm3, Z=1, Dc=1.816 Mg/m3, F(000)=512, μ=1.217 mm-1, S=0.946, the final R=0.0238 and wR=0.0631. Complex 2 crystallizes in monoclinic, space group P21/c, a=0.737(5), b=2.338(1), c=1.0030(6) nm, β=96.359(9)°, V=1.803(2) nm3, Z=4, Dc=1.826 Mg/m3, F(000)=984, μ=1.260 mm-1, S=1.016, the final R=0.0455 and wR=0.1007. Complex 1 exhibits a discrete cyclic binuclear structure and complex 2 possesses a 2D layer structure with cyclic binuclear unit. The fluorescent spectrum study shows that complex 1 exhibits fluorescent emission in the solid state at room temperature.
2015, 34(3): 393-400
doi: 10.14102/j.cnki.0254-5861.2011-0452
Abstract:
A new Co(Ⅱ) coordination polymer has been successfully synthesized under hydrothermal conditions [Co(C2O4)(mbix)]n (1, H2C2O4=oxalic acid, mbix=1,3-bis(imidazol-1-ylmethyl)benzene). Its structure has been determined by elemental analyses, IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Pink crystals crystallize in the triclinic system, space group P1 with a=8.8666(7), b=9.5859(8), c=10.8537(9)Å, α=67.6810(10), β=66.1260(10), γ=77.1300(10)°, V=777.77(11), C16H14CoN4O4, Mr=385.24, Dc=1.645 g/cm3, F(000)=394, Z=2, μ(MoKα)=1.134 mm-1, the final R=0.0482 and wR=0.1231 for 2968 observed reflections (I>2σ(I)). It shows a two-dimensional (2D) network structure. The intermolecular C-H…O hydrogen bonding and π-π stacking interactions extend complex 1 into a 3D supramolecular architecture and play an important role in stabilizing 1. In addition, Natural Bond Orbital (NBO) analysis was performed by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Co(Ⅱ) ion.
A new Co(Ⅱ) coordination polymer has been successfully synthesized under hydrothermal conditions [Co(C2O4)(mbix)]n (1, H2C2O4=oxalic acid, mbix=1,3-bis(imidazol-1-ylmethyl)benzene). Its structure has been determined by elemental analyses, IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Pink crystals crystallize in the triclinic system, space group P1 with a=8.8666(7), b=9.5859(8), c=10.8537(9)Å, α=67.6810(10), β=66.1260(10), γ=77.1300(10)°, V=777.77(11), C16H14CoN4O4, Mr=385.24, Dc=1.645 g/cm3, F(000)=394, Z=2, μ(MoKα)=1.134 mm-1, the final R=0.0482 and wR=0.1231 for 2968 observed reflections (I>2σ(I)). It shows a two-dimensional (2D) network structure. The intermolecular C-H…O hydrogen bonding and π-π stacking interactions extend complex 1 into a 3D supramolecular architecture and play an important role in stabilizing 1. In addition, Natural Bond Orbital (NBO) analysis was performed by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Co(Ⅱ) ion.
2015, 34(3): 401-407
doi: 10.14102/j.cnki.0254-5861.2011-0495
Abstract:
Redox reaction of a mixture of CuCl2·2H2O, H3PO3 and dpatrz (3,5-dipropyl-4-amino-1,2,4-triazole) at room temperature yields one new compound, [Cu(Ⅰ)(μ2-dpatrz)2Cu(Ⅰ)Cl2], with two independent cis-and trans-propyl side chain molecules. Compound 1 crystallizes in monoclinic, space group P21/c with a=7.474(1), b=17.807(1), c=18.851(1)Å, β=108.32(1)°, V=2381.7(2)Å3, Z=4, C16H32Cl2Cu2N8, Mr=534.48, Dc=1.491 g·cm-3, μ=2.03 mm-1, F(000)=1104, GOOF=1.050, the final R=0.0445 and wR=0.1162 for 3162 observed reflections (I>2σ(I)). Compound 1 shows discrete dimeric structures (A and B) containing inversion centers and the Cu(Ⅰ) ions are coordinated in triangle geometries. The isomers are connected by N-H…Cl hydrogen bonds, chains with graph-set C(7) and rings R22(14) and C-H…π interactions into stair-step chains (Tapes A and B) running parallel to the [01-1] direction. The N-H…Cl hydrogen bonds result in chain and cyclic structures with graph-sets C22(17) and R43(18) linking tapes A and B to form two-dimensional networks along the [031] direction. Packing of crystal 1 is stabilized by rings R43(18) and weak C-H…Cl hydrogen bonds parallel to the [01-2] direction. Bond valence sum (BVS) and UV-Vis absorption spectra support the existence of Cu(Ⅰ) ions. Compound 1 exhibits extensive green blue phosphorescence in the solid state at room temperature.
Redox reaction of a mixture of CuCl2·2H2O, H3PO3 and dpatrz (3,5-dipropyl-4-amino-1,2,4-triazole) at room temperature yields one new compound, [Cu(Ⅰ)(μ2-dpatrz)2Cu(Ⅰ)Cl2], with two independent cis-and trans-propyl side chain molecules. Compound 1 crystallizes in monoclinic, space group P21/c with a=7.474(1), b=17.807(1), c=18.851(1)Å, β=108.32(1)°, V=2381.7(2)Å3, Z=4, C16H32Cl2Cu2N8, Mr=534.48, Dc=1.491 g·cm-3, μ=2.03 mm-1, F(000)=1104, GOOF=1.050, the final R=0.0445 and wR=0.1162 for 3162 observed reflections (I>2σ(I)). Compound 1 shows discrete dimeric structures (A and B) containing inversion centers and the Cu(Ⅰ) ions are coordinated in triangle geometries. The isomers are connected by N-H…Cl hydrogen bonds, chains with graph-set C(7) and rings R22(14) and C-H…π interactions into stair-step chains (Tapes A and B) running parallel to the [01-1] direction. The N-H…Cl hydrogen bonds result in chain and cyclic structures with graph-sets C22(17) and R43(18) linking tapes A and B to form two-dimensional networks along the [031] direction. Packing of crystal 1 is stabilized by rings R43(18) and weak C-H…Cl hydrogen bonds parallel to the [01-2] direction. Bond valence sum (BVS) and UV-Vis absorption spectra support the existence of Cu(Ⅰ) ions. Compound 1 exhibits extensive green blue phosphorescence in the solid state at room temperature.
2015, 34(3): 408-416
doi: 10.14102/j.cnki.0254-5861.2011-0501
Abstract:
Two new coordination polymers [Cd(EBLA)(ip)(H2O)] (1) and [Ni(EBSA) (im)2(H2O)]n (2) were synthesized by hydrothermal and solution methods using 2,2'-dithiosalicylicacid (EBSA), 1H-imidazo[4,5-f][1,10]phenanthroline (ip), imidazole (im), Cd(NO3)2·4H2O and Ni(NO3)2·6H2O. The complexes were characterized by elemental analysis and FT-IR. Meanwhile, the crystal structures, fluorescence properties of complex 1 and thermogravimetrie analysis of complex 2 have been studied. In complex 1, 2,2'-dicarboxydiphenylthioether (EBLA) was prepared with 2,2'-dithiosalicylicacid (EBSA) in situ reaction by hydrothermal method. Complex 1 is a dinuclear structure and Cd2+ is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 is a one-dimensional infinite linear chain and Ni2+ is six-coordinated to form a distorted octahedral geometry. Hydrogen bonding and π-π interactions are observed in these complexes.
Two new coordination polymers [Cd(EBLA)(ip)(H2O)] (1) and [Ni(EBSA) (im)2(H2O)]n (2) were synthesized by hydrothermal and solution methods using 2,2'-dithiosalicylicacid (EBSA), 1H-imidazo[4,5-f][1,10]phenanthroline (ip), imidazole (im), Cd(NO3)2·4H2O and Ni(NO3)2·6H2O. The complexes were characterized by elemental analysis and FT-IR. Meanwhile, the crystal structures, fluorescence properties of complex 1 and thermogravimetrie analysis of complex 2 have been studied. In complex 1, 2,2'-dicarboxydiphenylthioether (EBLA) was prepared with 2,2'-dithiosalicylicacid (EBSA) in situ reaction by hydrothermal method. Complex 1 is a dinuclear structure and Cd2+ is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 is a one-dimensional infinite linear chain and Ni2+ is six-coordinated to form a distorted octahedral geometry. Hydrogen bonding and π-π interactions are observed in these complexes.
2015, 34(3): 417-422
doi: 10.14102/j.cnki.0254-5861.2011-0050
Abstract:
The reaction of flexible bis(imidazole) ligand and 1,2-bis(imidazol-1'-yl)methane (bimm) with Co(Ⅱ) salt under ionothermal method resulted in the formation of a new coordination polymer {[Co(bimm)3]·(PF6)2}n (1). X-ray single-crystal diffraction determination reveals that 1 crystallizes in the triclinic P1 space group, with a=8.647(6), b=12.092(9), c=14.967(11)Å, α=88.912(8), β=81.199(8), γ=89.395(8)°, V=1546(2)Å3, Z=2, Mr=793.39, Dc=1.704 Mg/m3, μ=0.768 mm-1, F(000)=798, the final R=0.0626 and wR=0.1634 for 4319 observed reflections with I>2σ(I). In compound 1, the Co(Ⅱ) ion is connected to another Co(Ⅱ) by two bimm ligands to form 1D double chains which are further linked by bimm ligands to form a 2D wavelike layer. Topologically, the structure of 1 represents a uninodal 2D 4-connected sql/Shubnikov tetragonal plane net. Moreover, thermogravimetric analyses and photocatalytic property for 1 have also been investigated.
The reaction of flexible bis(imidazole) ligand and 1,2-bis(imidazol-1'-yl)methane (bimm) with Co(Ⅱ) salt under ionothermal method resulted in the formation of a new coordination polymer {[Co(bimm)3]·(PF6)2}n (1). X-ray single-crystal diffraction determination reveals that 1 crystallizes in the triclinic P1 space group, with a=8.647(6), b=12.092(9), c=14.967(11)Å, α=88.912(8), β=81.199(8), γ=89.395(8)°, V=1546(2)Å3, Z=2, Mr=793.39, Dc=1.704 Mg/m3, μ=0.768 mm-1, F(000)=798, the final R=0.0626 and wR=0.1634 for 4319 observed reflections with I>2σ(I). In compound 1, the Co(Ⅱ) ion is connected to another Co(Ⅱ) by two bimm ligands to form 1D double chains which are further linked by bimm ligands to form a 2D wavelike layer. Topologically, the structure of 1 represents a uninodal 2D 4-connected sql/Shubnikov tetragonal plane net. Moreover, thermogravimetric analyses and photocatalytic property for 1 have also been investigated.
2015, 34(3): 423-427
doi: 10.14102/j.cnki.0254-5861.2011-0533
Abstract:
ZnC6H8N2O5.H2O (NCGZn) has been synthesized, and its functional groups present in the title compound were confirmed by elemental analysis, TG and IR spectral studies. Meanwhile, the crystal of NCGZn was obtained by slow evaporation of a saturated aqueous solution at room temperature and confirmed by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P21 with a=5.03220(1), b=13.3747(4), c=12.9944(4)Å, β=92.987(2)°, V=873.39(4)Å3, Z=2, C12H20N4O12Zn2, Mr=543.10, Dc=2.065 g/cm3, F(000)=552, μ(MoKa)=2.826 mm-1, R=0.0422 and wR=0.1142. In NCGZn, Zn(1) and the symmetry formed Zn(1) ions are connected by five atoms from four NCG-2H anions and a water molecule. A NCG ligand has two carboxylate groups, one connecting a Zn ion, and the other bridgiong two Zn ions. The NCG ligand bridges four Zn ions through the amino group and two carboxylate groups with a water molecule to yield a 3D coordination polymer structure with hydrogen bonds.
ZnC6H8N2O5.H2O (NCGZn) has been synthesized, and its functional groups present in the title compound were confirmed by elemental analysis, TG and IR spectral studies. Meanwhile, the crystal of NCGZn was obtained by slow evaporation of a saturated aqueous solution at room temperature and confirmed by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P21 with a=5.03220(1), b=13.3747(4), c=12.9944(4)Å, β=92.987(2)°, V=873.39(4)Å3, Z=2, C12H20N4O12Zn2, Mr=543.10, Dc=2.065 g/cm3, F(000)=552, μ(MoKa)=2.826 mm-1, R=0.0422 and wR=0.1142. In NCGZn, Zn(1) and the symmetry formed Zn(1) ions are connected by five atoms from four NCG-2H anions and a water molecule. A NCG ligand has two carboxylate groups, one connecting a Zn ion, and the other bridgiong two Zn ions. The NCG ligand bridges four Zn ions through the amino group and two carboxylate groups with a water molecule to yield a 3D coordination polymer structure with hydrogen bonds.
2015, 34(3): 428-434
doi: 10.14102/j.cnki.0254-5861.2011-0527
Abstract:
A new Sr(Ⅱ) complex, [Sr(Hsip)(H2O)] (1, NaH2sip=5-sulfoisophthalic acid monosodium), has been synthesized by solvothermal reaction of SrCO3 and NaH2sip at 120℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Singlecrystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr(Ⅱ) ion in 1. The coordination geometry of Sr(Ⅱ) is a distorted tetragonal anti-prism. The whole Hsip2- ligand performs a μ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.
A new Sr(Ⅱ) complex, [Sr(Hsip)(H2O)] (1, NaH2sip=5-sulfoisophthalic acid monosodium), has been synthesized by solvothermal reaction of SrCO3 and NaH2sip at 120℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Singlecrystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr(Ⅱ) ion in 1. The coordination geometry of Sr(Ⅱ) is a distorted tetragonal anti-prism. The whole Hsip2- ligand performs a μ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.
2015, 34(3): 435-440
doi: 10.14102/j.cnki.0254-5861.2011-0529
Abstract:
Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co(en)3]2[Zr2(C2O4)7]·2H2O (1) has been obtained. The title complex crystallizes in the monoclinic, space group P21/n (No. 14) with a=7.7448(10), b=14.5683(19), c=19.375(3)Å, β=92.124(2)°, V=2184.5(5)Å3, Z=4, Dc=1.996 g·cm-3, F(000)=1332, μ=1.328 mm-1, R=0.0353 and wR=0.0718 (I>2σ(I)). Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2(C2O4)7]6- and metal complexes Co(en)33+.
Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co(en)3]2[Zr2(C2O4)7]·2H2O (1) has been obtained. The title complex crystallizes in the monoclinic, space group P21/n (No. 14) with a=7.7448(10), b=14.5683(19), c=19.375(3)Å, β=92.124(2)°, V=2184.5(5)Å3, Z=4, Dc=1.996 g·cm-3, F(000)=1332, μ=1.328 mm-1, R=0.0353 and wR=0.0718 (I>2σ(I)). Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2(C2O4)7]6- and metal complexes Co(en)33+.
2015, 34(3): 441-446
doi: 10.14102/j.cnki.0254-5861.2011-0550
Abstract:
A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH (1, H3L=N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a=11.4400(8), b=22.9705(2), c=12.5712(9)Å, V=3303.5(4)Å3, Z=4, F(000)=1576, Dc=1.531 g·cm-3, Mr=761.36, μ=1.007 mm-1, S=1.014, the final R=0.0505 and wR=0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J=19.7 cm-1, g=1.89 and R2=0.9999.
A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH (1, H3L=N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a=11.4400(8), b=22.9705(2), c=12.5712(9)Å, V=3303.5(4)Å3, Z=4, F(000)=1576, Dc=1.531 g·cm-3, Mr=761.36, μ=1.007 mm-1, S=1.014, the final R=0.0505 and wR=0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J=19.7 cm-1, g=1.89 and R2=0.9999.
2015, 34(3): 447-452
doi: 10.14102/j.cnki.0254-5861.2011-0519
Abstract:
The title complex bis{1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthalenolato-N,O}-nickel(Ⅱ) (C36H32N4O2Ni) has been synthesized by the reaction of 1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthalenol with Ni(CH3COO)2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a=11.410(4), b=14.382(4), c=18.121(6)Å, β=97.147(6)°, V=2950.5(16)Å3, C36H32N4O2Ni, Mr=611.37, Z=4, Dc=1.376 g/cm3, μ=0.698 mm-1, F(000)=1280, the final R=0.0519 and wR=0.1493 (I>2σ(I)). This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98×107g of PNB (mol of Ni) h with high monomer conversion.
The title complex bis{1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthalenolato-N,O}-nickel(Ⅱ) (C36H32N4O2Ni) has been synthesized by the reaction of 1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthalenol with Ni(CH3COO)2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a=11.410(4), b=14.382(4), c=18.121(6)Å, β=97.147(6)°, V=2950.5(16)Å3, C36H32N4O2Ni, Mr=611.37, Z=4, Dc=1.376 g/cm3, μ=0.698 mm-1, F(000)=1280, the final R=0.0519 and wR=0.1493 (I>2σ(I)). This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98×107g of PNB (mol of Ni) h with high monomer conversion.
2015, 34(3): 453-460
doi: 10.14102/j.cnki.0254-5861.2011-0386
Abstract:
Ammonium 5-sulfosalicylic acid monohydrate (NH4·C7H5O6S·H2O, ASSA) was synthesized and optical grade crystal with dimensions of 45mm×20mm×18mm was obtained from aqueous solution by the cooling solution method. The crystal structure was confirmed by X-ray single-crystal diffraction method and the empirical composition is C7H11NO7S with formula weight 253.23. The crystal belongs to monoclinic space group P21/c with a=11.884(9), b=7.306(5), c=12.152(9)Å, β=104.851(13)°, V=1019.8(13)Å3, Z=4, Dc=1.649 g/cm3, μ=0.340 mm-1, F(000)=528, the final R=0.0307 and wR=0.0866 for 7494 observed reflections (I>2σ(I)). Elemental analysis, IR and 1H-NMR spectrum were used to characterize the compound. Thermal analysis showed that one coordination water molecule was contained and dehydration temperature of ASSA crystal was 106℃. Optical transmission and fluorescence spectrum revealed that the ASSA crystal exhibited a strong absorption in ultraviolet region with the sharp absorption edge located at 340 nm and a significant blue fluorescent emission band at 442 nm.
Ammonium 5-sulfosalicylic acid monohydrate (NH4·C7H5O6S·H2O, ASSA) was synthesized and optical grade crystal with dimensions of 45mm×20mm×18mm was obtained from aqueous solution by the cooling solution method. The crystal structure was confirmed by X-ray single-crystal diffraction method and the empirical composition is C7H11NO7S with formula weight 253.23. The crystal belongs to monoclinic space group P21/c with a=11.884(9), b=7.306(5), c=12.152(9)Å, β=104.851(13)°, V=1019.8(13)Å3, Z=4, Dc=1.649 g/cm3, μ=0.340 mm-1, F(000)=528, the final R=0.0307 and wR=0.0866 for 7494 observed reflections (I>2σ(I)). Elemental analysis, IR and 1H-NMR spectrum were used to characterize the compound. Thermal analysis showed that one coordination water molecule was contained and dehydration temperature of ASSA crystal was 106℃. Optical transmission and fluorescence spectrum revealed that the ASSA crystal exhibited a strong absorption in ultraviolet region with the sharp absorption edge located at 340 nm and a significant blue fluorescent emission band at 442 nm.
