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2015 Volume 34 Issue 2
2015, 34(2): 167-178
doi: 10.14102/j.cnki.0254-5861.2011-0480
Abstract:
A dynamic method is employed to study the reaction mechanisms of CH3CH2OCF3 with the hydrogen trioxy (HOOO) radical. In our paper, the geometries and harmonic vibrational frequencies of all the stationary points and minimum energy paths (MEPs) are calculated at the MPW1K/6-31+G(d,p) level of theory, and the energetic information along MEPs is further refined by the CCSD/6-31+G(df,p) level of theory. The rate constants are evaluated with the conventional transition-state theory (TST), the canonical variational transition-state theory (CVT), the microcanonical variational transition-state theory (μVT), the CVT coupled with the small-curvature tunneling (SCT) correction (CVT/SCT), and the μVT coupled with the Eckart tunneling correction (μVT/Eckart) based on the ab initio calculations in the temperature range of 200~3000 K. The theoretical results are important in determining the atmospheric lifetime and the feasible pathways for the loss of HFEs.
A dynamic method is employed to study the reaction mechanisms of CH3CH2OCF3 with the hydrogen trioxy (HOOO) radical. In our paper, the geometries and harmonic vibrational frequencies of all the stationary points and minimum energy paths (MEPs) are calculated at the MPW1K/6-31+G(d,p) level of theory, and the energetic information along MEPs is further refined by the CCSD/6-31+G(df,p) level of theory. The rate constants are evaluated with the conventional transition-state theory (TST), the canonical variational transition-state theory (CVT), the microcanonical variational transition-state theory (μVT), the CVT coupled with the small-curvature tunneling (SCT) correction (CVT/SCT), and the μVT coupled with the Eckart tunneling correction (μVT/Eckart) based on the ab initio calculations in the temperature range of 200~3000 K. The theoretical results are important in determining the atmospheric lifetime and the feasible pathways for the loss of HFEs.
2015, 34(2): 179-184
doi: 10.14102/j.cnki.0254-5861.2011-0394
Abstract:
A new series of 11-pyridyl substituted dibenzo-diazepin-1-one derivatives 1 was synthesized by a two step cyclocondensation reaction. All the compounds were characterized by IR, MS, and 1H NMR. And crystals of 1a and 1b were obtained and determined by X-ray single-crystal diffraction. Crystal data of 1a: C48H52N6O7, monoclinic system, space group C2/c, a=28.39(4), b=9.275(12), c=16.84(2)Å, β=104.98(3)°, V=4284(10)Å3, Z=4, F(000)=1752, Dc=1.279 g/cm3, R=0.0603, and wR=0.1314. Crystal data of 1b: C24H21N3O, monoclinic system, space group P21/c, a=11.625(5), b=19.055(9), c=8.741(4)Å, β=95.547(6)°, V=1927.2(15)Å3, Z=4, F(000)=776, Dc=1.266 g/cm3, R=0.0494, and wR=0.1287.
A new series of 11-pyridyl substituted dibenzo-diazepin-1-one derivatives 1 was synthesized by a two step cyclocondensation reaction. All the compounds were characterized by IR, MS, and 1H NMR. And crystals of 1a and 1b were obtained and determined by X-ray single-crystal diffraction. Crystal data of 1a: C48H52N6O7, monoclinic system, space group C2/c, a=28.39(4), b=9.275(12), c=16.84(2)Å, β=104.98(3)°, V=4284(10)Å3, Z=4, F(000)=1752, Dc=1.279 g/cm3, R=0.0603, and wR=0.1314. Crystal data of 1b: C24H21N3O, monoclinic system, space group P21/c, a=11.625(5), b=19.055(9), c=8.741(4)Å, β=95.547(6)°, V=1927.2(15)Å3, Z=4, F(000)=776, Dc=1.266 g/cm3, R=0.0494, and wR=0.1287.
2015, 34(2): 185-188
doi: 10.14102/j.cnki.0254-5861.2011-0443
Abstract:
Two novel pyran annulated heterocyclic compounds (1 and 2) were synthesized and characterized via IR, 1H NMR and H RMS. The structure of compound 1 was verified by single-crystal X-ray diffraction. The in vitro antibacterial activities of the two compounds against Staphylococcus aureus (S. aureus ATCC 29213), methicillin-resistant S. aureus (MRSA XJ 75302), vancomycin-intermediate S. aureus (Mu50 ATCC 700699), and USA 300 (Los Angeles County clone, LAC) were evaluated by observing the minimum inhibitory concentration.
Two novel pyran annulated heterocyclic compounds (1 and 2) were synthesized and characterized via IR, 1H NMR and H RMS. The structure of compound 1 was verified by single-crystal X-ray diffraction. The in vitro antibacterial activities of the two compounds against Staphylococcus aureus (S. aureus ATCC 29213), methicillin-resistant S. aureus (MRSA XJ 75302), vancomycin-intermediate S. aureus (Mu50 ATCC 700699), and USA 300 (Los Angeles County clone, LAC) were evaluated by observing the minimum inhibitory concentration.
2015, 34(2): 189-196
doi: 10.14102/j.cnki.0254-5861.2011-0467
Abstract:
3-Methyl-5-(2-methylphenyl)-1,3,4-oxadiazol-2(3H)-one (6) and N,N-diethyl-2-(2-methylbenzoyl)-hydrazinecarboxamide (7) were designed and synthesized from 5-(2-methylphenyl)-1,3,4-oxadiazol-2(3H)-one (5) by substituting and ring-opening, respectively. The target compounds were confirmed by IR, 1H NMR spectroscopy, MS, elemental analysis and single-crystal X-ray diffraction. Compound 6 (C10H10N2O2, Mr=190.20) crystallizes in the triclinic system, space group P1 with a=7.4645(16), b=10.868(2), c=12.970(3)Å, α=110.542(2), β=98.142(2), γ=99.766(2)°, V=947.7(3)Å3, Z=4, F(000)=400, Dc=1.333 g/cm3, μ=0.095 mm-1, the final R=0.0550 and wR=0.1483 for 2956 observed reflections with I>2σ(I). Compound 7 (C13H19N3O2, Mr=249.31) crystallizes in the monoclinic system, space group C2/c with a=18.926(3), b=12.1853(17), c=14.740(2)Å, β=125.6380(10)°, V=2762.7(7)Å3, Z=8, F(000)=1072, Dc=1.199 g/cm3, μ=0.083 mm-1, the final R=0.0554 and wR=0.1468 for 2395 observed reflections with I>2σ(I). The preliminary bioassay results indicate that compound 6 exhibits notable fungicidal activities against Fusarium graminearum, Botrytis cinerea, Rhizoctonia cerealis and Colletotrichum capsici at the concentration of 100 μg/mL.
3-Methyl-5-(2-methylphenyl)-1,3,4-oxadiazol-2(3H)-one (6) and N,N-diethyl-2-(2-methylbenzoyl)-hydrazinecarboxamide (7) were designed and synthesized from 5-(2-methylphenyl)-1,3,4-oxadiazol-2(3H)-one (5) by substituting and ring-opening, respectively. The target compounds were confirmed by IR, 1H NMR spectroscopy, MS, elemental analysis and single-crystal X-ray diffraction. Compound 6 (C10H10N2O2, Mr=190.20) crystallizes in the triclinic system, space group P1 with a=7.4645(16), b=10.868(2), c=12.970(3)Å, α=110.542(2), β=98.142(2), γ=99.766(2)°, V=947.7(3)Å3, Z=4, F(000)=400, Dc=1.333 g/cm3, μ=0.095 mm-1, the final R=0.0550 and wR=0.1483 for 2956 observed reflections with I>2σ(I). Compound 7 (C13H19N3O2, Mr=249.31) crystallizes in the monoclinic system, space group C2/c with a=18.926(3), b=12.1853(17), c=14.740(2)Å, β=125.6380(10)°, V=2762.7(7)Å3, Z=8, F(000)=1072, Dc=1.199 g/cm3, μ=0.083 mm-1, the final R=0.0554 and wR=0.1468 for 2395 observed reflections with I>2σ(I). The preliminary bioassay results indicate that compound 6 exhibits notable fungicidal activities against Fusarium graminearum, Botrytis cinerea, Rhizoctonia cerealis and Colletotrichum capsici at the concentration of 100 μg/mL.
2015, 34(2): 197-202
doi: 10.14102/j.cnki.0254-5861.2011-0471
Abstract:
A Schiff base was synthesized by 3-methyl-4-amino-5-ethoxycarbonyl-methylsulfanyl-1,2,4-triazole with 3-nitrobenzaldehyde. The structure was confirmed by 1H NMR, IR, H RMS, TGA techniques and X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c, with a=8.965(2), b=21.903(5), c=9.197(2)Å, β=114.011(4)°, C14H15N5O4S, Mr=349.08, V=1649.7(6)Å3, Dc=1.407 g·cm-3, Z=4, F(000)=728, μ=0.226 mm-1, the final R=0.0574 and wR=0.1336 for 2932 unique reflections with I>2σ(I). Furthermore, the biological activity to four vegetable pathogens has been tested. The title compound exhibits better biological activity to four vegetable pathogens compared to the Schiff base without 5-ethoxycarbonyl and to Gibberlla saubinetti in EC95 compared with triadimefon.
A Schiff base was synthesized by 3-methyl-4-amino-5-ethoxycarbonyl-methylsulfanyl-1,2,4-triazole with 3-nitrobenzaldehyde. The structure was confirmed by 1H NMR, IR, H RMS, TGA techniques and X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c, with a=8.965(2), b=21.903(5), c=9.197(2)Å, β=114.011(4)°, C14H15N5O4S, Mr=349.08, V=1649.7(6)Å3, Dc=1.407 g·cm-3, Z=4, F(000)=728, μ=0.226 mm-1, the final R=0.0574 and wR=0.1336 for 2932 unique reflections with I>2σ(I). Furthermore, the biological activity to four vegetable pathogens has been tested. The title compound exhibits better biological activity to four vegetable pathogens compared to the Schiff base without 5-ethoxycarbonyl and to Gibberlla saubinetti in EC95 compared with triadimefon.
2015, 34(2): 203-207
doi: 10.14102/j.cnki.0254-5861.2011-0481
Abstract:
The title compound 4-(5-((2,4-dichlorobenzyl)thio)-4-phenyl-4H-1,2,4-triazol-3-yl)pyridine (C20H14Cl2N4S) was synthesized, and its structure was confirmed by 1H NMR, MS, elemental analyses and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a=14.885(5), b=8.597(2), c=16.144(5)Å, β=114.505(4)°, V=1879.8(10)Å3, Z=8 and R=0.0320 for 3108 observed reflections with I>2σ(I). The preliminary biological test shows that the title compound has activities against Stemphylium lycopersici (Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea with inhibitory to be 53.57%, 66.67% and 24.44%, respectively.
The title compound 4-(5-((2,4-dichlorobenzyl)thio)-4-phenyl-4H-1,2,4-triazol-3-yl)pyridine (C20H14Cl2N4S) was synthesized, and its structure was confirmed by 1H NMR, MS, elemental analyses and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a=14.885(5), b=8.597(2), c=16.144(5)Å, β=114.505(4)°, V=1879.8(10)Å3, Z=8 and R=0.0320 for 3108 observed reflections with I>2σ(I). The preliminary biological test shows that the title compound has activities against Stemphylium lycopersici (Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea with inhibitory to be 53.57%, 66.67% and 24.44%, respectively.
2015, 34(2): 208-214
doi: 10.14102/j.cnki.0254-5861.2011-0472
Abstract:
A new photochromic diarylethene, [1-(2-methyl-5-(4-cyanophenyl)-3-thienyl-2-(2-methyl-5-phenyl-3-thienyl)]perfluorocyclopentene (1o, C28H17F6NS2), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its crystal belongs to the monoclinic system, space group P21/c with a=24.1381(5), b=9.3834(6), c=11.1073(8), β=94.477(4)°, Z=4, V=2508.1(3)Å3, Dc=1.445 mg/m3, μ=0.275, F(000)=1112, the final R=0.0482 and wR=0.1429 for 5834 observed reflections (I>2σ(I)). Further study demonstrated the diarylethene underwent reversible photochromism, changing between colorless and blue in hexane solution, crystalline phase and PMMA films, respectively.
A new photochromic diarylethene, [1-(2-methyl-5-(4-cyanophenyl)-3-thienyl-2-(2-methyl-5-phenyl-3-thienyl)]perfluorocyclopentene (1o, C28H17F6NS2), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its crystal belongs to the monoclinic system, space group P21/c with a=24.1381(5), b=9.3834(6), c=11.1073(8), β=94.477(4)°, Z=4, V=2508.1(3)Å3, Dc=1.445 mg/m3, μ=0.275, F(000)=1112, the final R=0.0482 and wR=0.1429 for 5834 observed reflections (I>2σ(I)). Further study demonstrated the diarylethene underwent reversible photochromism, changing between colorless and blue in hexane solution, crystalline phase and PMMA films, respectively.
2015, 34(2): 215-220
doi: 10.14102/j.cnki.0254-5861.2011-0463
Abstract:
A novel pyridine-contained α-cyanostilbenzene Schiff base, (Z)-3-(4-butoxyphenyl)-2-(4-((E)-pyridin-2-yl-methyleneamino)phenyl)acrylonitrile (L), has been synthesized and characterized by 1H NMR, 13C NMR, FT-IR spectra and single-crystal X-ray diffraction. Single-crystal data show that compound L belongs to the triclinic system, space group P1, with a=8.759(4), b=10.779(4), c=12.594(5)Å, α=65.873(4), β=88.332(5), γ=73.800(5)°, Mr=381.46, V=1037.2(7)Å3, Z=2, Dc=1.221 g/cm-3, μ=0.076 mm-1, F(000)=404, Rint=0.0311, R (I>2σ(I))=0.0484, wR (I>2σ(I))=0.1544, R (all data)=0.0484, wR (all data)=0.1692, completeness to theta=25.000 being 99.0% and GOF=1.179. There are two kinds of intermolecular hydrogen bonds and one kind of C-H…π weak interaction between adjacent molecules. Compound L can be used as a candidate for desirable devices with high performance due to its good thermal stability and excellent optical performance.
A novel pyridine-contained α-cyanostilbenzene Schiff base, (Z)-3-(4-butoxyphenyl)-2-(4-((E)-pyridin-2-yl-methyleneamino)phenyl)acrylonitrile (L), has been synthesized and characterized by 1H NMR, 13C NMR, FT-IR spectra and single-crystal X-ray diffraction. Single-crystal data show that compound L belongs to the triclinic system, space group P1, with a=8.759(4), b=10.779(4), c=12.594(5)Å, α=65.873(4), β=88.332(5), γ=73.800(5)°, Mr=381.46, V=1037.2(7)Å3, Z=2, Dc=1.221 g/cm-3, μ=0.076 mm-1, F(000)=404, Rint=0.0311, R (I>2σ(I))=0.0484, wR (I>2σ(I))=0.1544, R (all data)=0.0484, wR (all data)=0.1692, completeness to theta=25.000 being 99.0% and GOF=1.179. There are two kinds of intermolecular hydrogen bonds and one kind of C-H…π weak interaction between adjacent molecules. Compound L can be used as a candidate for desirable devices with high performance due to its good thermal stability and excellent optical performance.
2015, 34(2): 221-226
doi: 10.14102/j.cnki.0254-5861.2011-0446
Abstract:
A novel metal-organic coordination complex [Zn(CHIP)(AIC)]n (1, CHIP=2-(4-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, AIC=5-amino-isophthalic acid) has been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a=18.259(5), b=17.191(4), c=16.371(4)Å, V=4717(2)Å3, C27H16ClN5O4Zn, Mr=575.29, Dc=1.620 g/cm3, μ(MoKα)=1.202 mm-1, F(000)=2335, Z=8, the final R=0.032 and wR=0.074 for 4723 observed reflections (I>2σ(I)). Single-crystal X-ray diffraction reveals that 1 exhibits one-dimensional (1D) double chains, which are linked by H-bond intersections into a 2D structure. TG analysis shows clear weight loss due to the decomposition of different ligands. The luminescent properties for the ligand and complex 1 were also studied.
A novel metal-organic coordination complex [Zn(CHIP)(AIC)]n (1, CHIP=2-(4-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, AIC=5-amino-isophthalic acid) has been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a=18.259(5), b=17.191(4), c=16.371(4)Å, V=4717(2)Å3, C27H16ClN5O4Zn, Mr=575.29, Dc=1.620 g/cm3, μ(MoKα)=1.202 mm-1, F(000)=2335, Z=8, the final R=0.032 and wR=0.074 for 4723 observed reflections (I>2σ(I)). Single-crystal X-ray diffraction reveals that 1 exhibits one-dimensional (1D) double chains, which are linked by H-bond intersections into a 2D structure. TG analysis shows clear weight loss due to the decomposition of different ligands. The luminescent properties for the ligand and complex 1 were also studied.
2015, 34(2): 227-234
doi: 10.14102/j.cnki.0254-5861.2011-0455
Abstract:
Two coordination compounds, namely [Ce(3,5-Br2BC)3(3,5-HBr2BC)]n (1) and [Zn(3,5-Br2BC)2(phen)] (2, 3,5-HBr2BC=3,5-dibromobenzoic acid, phen=1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via Br…Br and Br…O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H…O hydrogen bond, π-π stacking interactions and Br…π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.
Two coordination compounds, namely [Ce(3,5-Br2BC)3(3,5-HBr2BC)]n (1) and [Zn(3,5-Br2BC)2(phen)] (2, 3,5-HBr2BC=3,5-dibromobenzoic acid, phen=1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via Br…Br and Br…O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H…O hydrogen bond, π-π stacking interactions and Br…π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.
2015, 34(2): 235-240
doi: 10.14102/j.cnki.0254-5861.2011-462
Abstract:
A new Zn(Ⅱ) coordination polymer [Zn3(BTC)2(4,4'-bpy)(CO)2]n (1, H3BTC=1,3,5-benzenetricarboxylic acid, 4,4'-bpy=4,4'-bipyridine) has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a=10.262(3), b=18.838(5), c=15.083(4)Å, β=99.203(4)°, V=2878.3(14)Å3, C30H14Zn3N2O14, Mr=822.54, Z=4, Dc=1.898 g/cm3, μ=2.561 mm-1, F(000)=1640, R=0.0363 and wR=0.0932 for 2828 observed reflections (I>2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(Ⅱ) atoms which are connected by BTC3- ligands and 4,4'-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.
A new Zn(Ⅱ) coordination polymer [Zn3(BTC)2(4,4'-bpy)(CO)2]n (1, H3BTC=1,3,5-benzenetricarboxylic acid, 4,4'-bpy=4,4'-bipyridine) has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a=10.262(3), b=18.838(5), c=15.083(4)Å, β=99.203(4)°, V=2878.3(14)Å3, C30H14Zn3N2O14, Mr=822.54, Z=4, Dc=1.898 g/cm3, μ=2.561 mm-1, F(000)=1640, R=0.0363 and wR=0.0932 for 2828 observed reflections (I>2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(Ⅱ) atoms which are connected by BTC3- ligands and 4,4'-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.
2015, 34(2): 241-247
doi: 10.14102/j.cnki.0254-5861.2011-0416
Abstract:
Two new 2D coordination polymers, [Zn(HL)(Hbpp)]n (1) and [Cd(HL)(Hbpp)(H2O)]n (2) (H4L=1,3-di(2,4-dicarboxyphenyl) benzene, bpp=1,3-di(4-pyridyl)propane), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, TGA and IR spectroscopy. Complex 1 crystallizes in monoclinic, space group P21/n, with a=13.1031(6), b=14.7315(7), c=15.0041(7)Å, β=91.202(1)°, V=2895.6(2)Å3, Dc=1.532 g/cm3, Mr=667.97, F(000)=1376.0, μ=0.909 mm-1, Z=4, the final R=0.0481 and wR=0.1304 for 7027 observed reflections with I>2σ(I). Complex 2 also belongs to the monoclinic space group P21/n, with a=13.6326(4), b=14.6432(4), c=14.9395(5)Å, β=93.132(1)°, V=2977.84(16)Å3, Dc=1.613 g/cm3, Mr=1445.98, F(000)=733.0, μ=0.794 mm-1, Z=2, the final R=0.0283 and wR=0.0784 for 7230 observed reflections with I>2σ(I). Both complexes 1 and 2 form 2D net structures, which are further linked to form 3D supramolecular net structures via intermolecular hydrogen bonds and aromatic π-π stacking interactions.
Two new 2D coordination polymers, [Zn(HL)(Hbpp)]n (1) and [Cd(HL)(Hbpp)(H2O)]n (2) (H4L=1,3-di(2,4-dicarboxyphenyl) benzene, bpp=1,3-di(4-pyridyl)propane), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, TGA and IR spectroscopy. Complex 1 crystallizes in monoclinic, space group P21/n, with a=13.1031(6), b=14.7315(7), c=15.0041(7)Å, β=91.202(1)°, V=2895.6(2)Å3, Dc=1.532 g/cm3, Mr=667.97, F(000)=1376.0, μ=0.909 mm-1, Z=4, the final R=0.0481 and wR=0.1304 for 7027 observed reflections with I>2σ(I). Complex 2 also belongs to the monoclinic space group P21/n, with a=13.6326(4), b=14.6432(4), c=14.9395(5)Å, β=93.132(1)°, V=2977.84(16)Å3, Dc=1.613 g/cm3, Mr=1445.98, F(000)=733.0, μ=0.794 mm-1, Z=2, the final R=0.0283 and wR=0.0784 for 7230 observed reflections with I>2σ(I). Both complexes 1 and 2 form 2D net structures, which are further linked to form 3D supramolecular net structures via intermolecular hydrogen bonds and aromatic π-π stacking interactions.
2015, 34(2): 248-252
doi: 10.14102/j.cnki.0254-5861.2011-0449
Abstract:
A new Cd(Ⅱ) coordination polymer, namely, [Cd(1,3-bip)(3,5-pdc)]n (1,3-bip=1,3-bis(imidazol)propane and 3,5-pdc=pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a=1.40178(7), b=1.72502(12), c=1.41635(6) nm, β=92.653(4)°, V=3.4212(3) nm3, Z=4, C16H15CdN5O4, Mr=453.73, Dc=1.762 g/cm3, F(000)=1808, μ=1.310 mm-1, R=0.0899 and wR=0.1945. In compound 1, each 3,5-pdc ligand links three Cd(Ⅱ) ions and each Cd(Ⅱ) attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.
A new Cd(Ⅱ) coordination polymer, namely, [Cd(1,3-bip)(3,5-pdc)]n (1,3-bip=1,3-bis(imidazol)propane and 3,5-pdc=pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a=1.40178(7), b=1.72502(12), c=1.41635(6) nm, β=92.653(4)°, V=3.4212(3) nm3, Z=4, C16H15CdN5O4, Mr=453.73, Dc=1.762 g/cm3, F(000)=1808, μ=1.310 mm-1, R=0.0899 and wR=0.1945. In compound 1, each 3,5-pdc ligand links three Cd(Ⅱ) ions and each Cd(Ⅱ) attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.
2015, 34(2): 253-259
doi: 10.14102/j.cnki.0254-5861.2011-0461
Abstract:
A new energetic complex, Ni(3,4'-Hbpt)2(Hoba)2(H2O)2 (3,4'-Hbpt=3-(3-pyridyl)-5-(4'-pyridyl)-1-H-1,2,4-triazole and H2oba=4,4'-oxybis(benzoic acid)), has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P21/c with a=10.2357(9), b=24.594(2), c=10.4225(9)Å, β=114.0110(10)°, V=2396.7(4)Å3, Dc=1.460 g/cm3, μ=0.482 mm-1, Mr=1053.63, F(000)=1088, Z=2, the final R=0.0358 and wR=0.0973 with I>2σ(I). Both 3,4'-Hbpt and H2oba ligands adopt monodentate modes linking one Ni(Ⅱ) ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate (AP) is explored by differential scanning calorimetry (DSC), which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.
A new energetic complex, Ni(3,4'-Hbpt)2(Hoba)2(H2O)2 (3,4'-Hbpt=3-(3-pyridyl)-5-(4'-pyridyl)-1-H-1,2,4-triazole and H2oba=4,4'-oxybis(benzoic acid)), has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P21/c with a=10.2357(9), b=24.594(2), c=10.4225(9)Å, β=114.0110(10)°, V=2396.7(4)Å3, Dc=1.460 g/cm3, μ=0.482 mm-1, Mr=1053.63, F(000)=1088, Z=2, the final R=0.0358 and wR=0.0973 with I>2σ(I). Both 3,4'-Hbpt and H2oba ligands adopt monodentate modes linking one Ni(Ⅱ) ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate (AP) is explored by differential scanning calorimetry (DSC), which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.
2015, 34(2): 260-266
doi: 10.14102/j.cnki.0254-5861.2011-0464
Abstract:
A complex [Cd2(tbb)Cl4]·4DMF·3H2O, where tbb is 1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane, was synthesized and characterized by X-ray single-crystal structure analyses. For this complex: C44H49Cd2C14N12O7, Mr=1224.55, monoclinic system, space group C2/c, a=29.563(3), b=14.2580(17), c=26.355(3)Å, β=97.036(2)°, V=11025(2)Å3, Z=8, Dc=1.475 g/cm3, λ=0.71073Å, μ(MoKα)=1.021 mm-1, F(000)=4936, S=1.047, R=0.0680 and wR=0.1832 for 11812 observed reflections with I>2σ(I). It is a neutral dinuclear complex. One 1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane coordinates to two cadmium ions. Each cadmium ion is coordinated by two nitrogen atoms of tbb and two chloride ions. The complex emits blue luminescence in DMF solution as well as in solid powder state.
A complex [Cd2(tbb)Cl4]·4DMF·3H2O, where tbb is 1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane, was synthesized and characterized by X-ray single-crystal structure analyses. For this complex: C44H49Cd2C14N12O7, Mr=1224.55, monoclinic system, space group C2/c, a=29.563(3), b=14.2580(17), c=26.355(3)Å, β=97.036(2)°, V=11025(2)Å3, Z=8, Dc=1.475 g/cm3, λ=0.71073Å, μ(MoKα)=1.021 mm-1, F(000)=4936, S=1.047, R=0.0680 and wR=0.1832 for 11812 observed reflections with I>2σ(I). It is a neutral dinuclear complex. One 1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane coordinates to two cadmium ions. Each cadmium ion is coordinated by two nitrogen atoms of tbb and two chloride ions. The complex emits blue luminescence in DMF solution as well as in solid powder state.
2015, 34(2): 267-271
doi: 10.14102/j.cnki.0254-5861.2011-0477
Abstract:
A new Cd(Ⅱ) coordination polymer with 2-nitroterephthalic acid (H2npa) and 1,4-bis(2-methyl-imidazol-1-yl) butane (bib) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd(npa)(bib)]n (1) is of orthorhombic system, space group Pcca with a=16.1750(5), b=9.8764(5), c=15.5890(3)Å, V=2490.4(2)Å3, Z=4, Mr=539.82, Dc=1.440 g/cm3, F(000)=1088, μ=0.918 mm-1, the final R=0.0320 and wR=0.0775 for 2253 reflections with I>2σ(I). X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.
A new Cd(Ⅱ) coordination polymer with 2-nitroterephthalic acid (H2npa) and 1,4-bis(2-methyl-imidazol-1-yl) butane (bib) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd(npa)(bib)]n (1) is of orthorhombic system, space group Pcca with a=16.1750(5), b=9.8764(5), c=15.5890(3)Å, V=2490.4(2)Å3, Z=4, Mr=539.82, Dc=1.440 g/cm3, F(000)=1088, μ=0.918 mm-1, the final R=0.0320 and wR=0.0775 for 2253 reflections with I>2σ(I). X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.
2015, 34(2): 272-278
doi: 10.14102/j.cnki.0254-5861.2011-0355
Abstract:
A new intermetallic compound, SmCu7.73In3.27, has been synthesized by solid-state reaction of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. SmCu7.73In3.27 crystallizes in tetragonal space group P4/mbm with a=8.6213(4), c=10.2538(9), V=762.13(8)Å3, Z=4, Mr=1018.90, Dc=8.880 g/cm3, μ=38.244 mm-1, F(000)=1789, and the final R=0.0374 and wR=0.0836 for 514 observed reflections with I>2σ(I). The structure of SmCu7.69In3.31 belongs to a new structure type and features a three-dimensional (3D) [Cu5In2M4] (M=Cu/In) framework composed of [Cu5In4M4] clusters interconnected via sharing In atoms as well as Cu-In and In-In bonds. The Sm atoms are located in the one-dimensional (1D) tunnels along the c-axis. The structural relationship of the title compound with other similar Sm-Cu-In phases was also studied. Band structure calculations based on Density Functional Theory (DFT) method indicate that SmCu7.69In3.31 is metallic.
A new intermetallic compound, SmCu7.73In3.27, has been synthesized by solid-state reaction of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. SmCu7.73In3.27 crystallizes in tetragonal space group P4/mbm with a=8.6213(4), c=10.2538(9), V=762.13(8)Å3, Z=4, Mr=1018.90, Dc=8.880 g/cm3, μ=38.244 mm-1, F(000)=1789, and the final R=0.0374 and wR=0.0836 for 514 observed reflections with I>2σ(I). The structure of SmCu7.69In3.31 belongs to a new structure type and features a three-dimensional (3D) [Cu5In2M4] (M=Cu/In) framework composed of [Cu5In4M4] clusters interconnected via sharing In atoms as well as Cu-In and In-In bonds. The Sm atoms are located in the one-dimensional (1D) tunnels along the c-axis. The structural relationship of the title compound with other similar Sm-Cu-In phases was also studied. Band structure calculations based on Density Functional Theory (DFT) method indicate that SmCu7.69In3.31 is metallic.
2015, 34(2): 279-284
doi: 10.14102/j.cnki.0254-5861.2011-0473
Abstract:
A new lanthanide porphyrin, [SmⅢ(H3TPPSⅢ)]n·nH2O (1, H6TPPS=tetra(4-sulfonatophenyl)porphyrin), has been synthesized through a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the P4/mcc space group of tetragonal system: a=15.3683(12), c=9.895(2)Å, V=2337.0(5)Å3, C44H29N4O13S4Sm, Mr=1100.30, Z=2, Dc=1.564 g/cm3, S=1.063, μ(MoKα)=1.502 mm-1, F(000)=1102, R=0.0583 and wR=0.1666. Compound 1 is characteristic of a three-dimensional (3-D) framework with a slightly distorted square-antiprism eight-coordinated Sm3+ ion. Fluorescent study revealed that compound 1 exhibits an emission in the red region. The fluorescence quantum yield and lifetime of 1 were determined to be 3.5% and 9.1 ns, respectively. UV-vis absorption spectra were also investigated.
A new lanthanide porphyrin, [SmⅢ(H3TPPSⅢ)]n·nH2O (1, H6TPPS=tetra(4-sulfonatophenyl)porphyrin), has been synthesized through a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the P4/mcc space group of tetragonal system: a=15.3683(12), c=9.895(2)Å, V=2337.0(5)Å3, C44H29N4O13S4Sm, Mr=1100.30, Z=2, Dc=1.564 g/cm3, S=1.063, μ(MoKα)=1.502 mm-1, F(000)=1102, R=0.0583 and wR=0.1666. Compound 1 is characteristic of a three-dimensional (3-D) framework with a slightly distorted square-antiprism eight-coordinated Sm3+ ion. Fluorescent study revealed that compound 1 exhibits an emission in the red region. The fluorescence quantum yield and lifetime of 1 were determined to be 3.5% and 9.1 ns, respectively. UV-vis absorption spectra were also investigated.
2015, 34(2): 285-291
doi: 10.14102/j.cnki.0254-5861.2011-0486
Abstract:
A new coordination polymer {[Ba(L)(H2O)5]·H2O}n (1, H2L=3,3'-((((ethane-1,2-diylbis(oxy))-bis(2,1-phenylene))bis(methylene))bis(oxy))dibenzoic acid) has been synthesized under evaporation process and characterized by elemental analysis, IR spectra, TG analysis, fluorescence spectrum, powder X-ray diffraction analysis and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c, with a=20.918(5), b=7.4539(2), c=20.168(5)Å, b=95.486(2)°, V=3130.1(1)Å3, Z=4, C30H34BaO14, Mr=755.91, Dc=1.604 g/cm3, F(000)=1528, μ=1.34 mm-1, the final R=0.0404 and wR=0.0676 for all data. Single-crystal X-ray structural reveals that the Ba(Ⅱ) ion adopts a nine-coordinated distorted tricapped trigonal prism coordination geometry. Adjacent Ba(Ⅱ) ions are linked by one μ2-L2-anion and two (μ2-H2O) water molecules to generate an infinite 1D zigzag chain structure. Then these chains are further linked into a 2D layer supramolecular architecture through O-H…O hydrogen bonds. Luminescent property and thermal stability of complex 1 were investigated.
A new coordination polymer {[Ba(L)(H2O)5]·H2O}n (1, H2L=3,3'-((((ethane-1,2-diylbis(oxy))-bis(2,1-phenylene))bis(methylene))bis(oxy))dibenzoic acid) has been synthesized under evaporation process and characterized by elemental analysis, IR spectra, TG analysis, fluorescence spectrum, powder X-ray diffraction analysis and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c, with a=20.918(5), b=7.4539(2), c=20.168(5)Å, b=95.486(2)°, V=3130.1(1)Å3, Z=4, C30H34BaO14, Mr=755.91, Dc=1.604 g/cm3, F(000)=1528, μ=1.34 mm-1, the final R=0.0404 and wR=0.0676 for all data. Single-crystal X-ray structural reveals that the Ba(Ⅱ) ion adopts a nine-coordinated distorted tricapped trigonal prism coordination geometry. Adjacent Ba(Ⅱ) ions are linked by one μ2-L2-anion and two (μ2-H2O) water molecules to generate an infinite 1D zigzag chain structure. Then these chains are further linked into a 2D layer supramolecular architecture through O-H…O hydrogen bonds. Luminescent property and thermal stability of complex 1 were investigated.
2015, 34(2): 292-298
doi: 10.14102/j.cnki.0254-5861.2011-0487
Abstract:
A new coordination polymer, [Zn2(m-bix)(p-bdc)2] (1), was synthesized under hydrothermal conditions by a reaction of 1,3-bis(imidazol-1-ylmethyl)benzene (m-bix), 1,3-benzenedicarboxylic acid (H2p-bdc) and Zn(NO3)2. The colorless block crystals of complex 1 (C30H22N4O8Zn2) belong to the triclinic system, space group P1 with a=10.213(2), b=12.052(2), c=12.392(3)Å, α=82.97(3), β=76.04(3), γ=78.02(3)°, V=1443.8(5)Å3, Z=2, Dc=1.604 g/cm-3, Mr=697.26, F(000)=708, R=0.0403 and wR=0.0907 for 4886 observed reflections (I>2σ(I)). In 1, the tetrahedral ZnⅡ cations are linked by [p-bdc]2- anions into 2D sq1 networks, which are further connected by bix ligands forming an interesting 2-fold 4,4-connected mog-type 3D network with a point symbol of {4·64·8}2{42·62·82}. Complex 1 was characterized by elemental, IR spectroscopy, powder X-ray diffractions and thermalgravimetric analysis. In addition, complex 1 exhibits coordination induced photoluminescent property.
A new coordination polymer, [Zn2(m-bix)(p-bdc)2] (1), was synthesized under hydrothermal conditions by a reaction of 1,3-bis(imidazol-1-ylmethyl)benzene (m-bix), 1,3-benzenedicarboxylic acid (H2p-bdc) and Zn(NO3)2. The colorless block crystals of complex 1 (C30H22N4O8Zn2) belong to the triclinic system, space group P1 with a=10.213(2), b=12.052(2), c=12.392(3)Å, α=82.97(3), β=76.04(3), γ=78.02(3)°, V=1443.8(5)Å3, Z=2, Dc=1.604 g/cm-3, Mr=697.26, F(000)=708, R=0.0403 and wR=0.0907 for 4886 observed reflections (I>2σ(I)). In 1, the tetrahedral ZnⅡ cations are linked by [p-bdc]2- anions into 2D sq1 networks, which are further connected by bix ligands forming an interesting 2-fold 4,4-connected mog-type 3D network with a point symbol of {4·64·8}2{42·62·82}. Complex 1 was characterized by elemental, IR spectroscopy, powder X-ray diffractions and thermalgravimetric analysis. In addition, complex 1 exhibits coordination induced photoluminescent property.
2015, 34(2): 299-305
doi: 10.14102/j.cnki.0254-5861.2011-0493
Abstract:
A new chain-like coordination polymer, namely, [CuL]n (1, Na2L=2-[(2-hydroxybenzylidene)-amino]-benzenesulfonic acid sodium salt), has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a=9.2296(16), b=10.4754(18), c=12.200(2)Å, β=102.392(2)°, V=1152.0(3)Å3, C13H9CuNO4S, Mr=338.83, Dc=1.953 g/cm3, Z=4, F(000)=684, μ=2.089 mm-1, the final R=0.0376 and wR=0.0956. X-ray diffraction analyses indicate that 1 displays a square-pyramidal metal center with NO4 donor sets. The sulfonate-derived Schiff base serves as a common N,O,O'-tridentate and a unique O-bridged ligand connecting the metals. Dinuclear copper complexes serve as secondary building blocks (SBUs) to construct an unusual 2D coordination network. In the crystal, the components form a stable 3D supramolecular architecture by C-H…O interactions and π-stacking.
A new chain-like coordination polymer, namely, [CuL]n (1, Na2L=2-[(2-hydroxybenzylidene)-amino]-benzenesulfonic acid sodium salt), has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a=9.2296(16), b=10.4754(18), c=12.200(2)Å, β=102.392(2)°, V=1152.0(3)Å3, C13H9CuNO4S, Mr=338.83, Dc=1.953 g/cm3, Z=4, F(000)=684, μ=2.089 mm-1, the final R=0.0376 and wR=0.0956. X-ray diffraction analyses indicate that 1 displays a square-pyramidal metal center with NO4 donor sets. The sulfonate-derived Schiff base serves as a common N,O,O'-tridentate and a unique O-bridged ligand connecting the metals. Dinuclear copper complexes serve as secondary building blocks (SBUs) to construct an unusual 2D coordination network. In the crystal, the components form a stable 3D supramolecular architecture by C-H…O interactions and π-stacking.
2015, 34(2): 306-312
doi: 10.14102/j.cnki.0254-5861.2011-2011-0507
Abstract:
Two new ion-pair complexes [Co(BBP)2]2[Ni(mnt)2]Cl2·4DMF·2H2O (1, BBP=2,6-bis(benzimidazol-2'-yl) pyridine, mnt=maleonitriledithiolate) and [(Py)2CH2][Co(mnt)2]2·4DMF (2) have been synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses and single-crystal X-ray diffraction. X-ray diffraction studies show that complex 1 crystallizes in monoclinic, space group P21/c. The crystal of 2 belongs to a triclinic system with space group P1. Due to the hydrogen bonding interactions, anions and cations formed the mixed packing in complex 1 while the anions and cations formed segregated columns in 2. In addition, thermogravimetric analyses of the two complexes are also investigated.
Two new ion-pair complexes [Co(BBP)2]2[Ni(mnt)2]Cl2·4DMF·2H2O (1, BBP=2,6-bis(benzimidazol-2'-yl) pyridine, mnt=maleonitriledithiolate) and [(Py)2CH2][Co(mnt)2]2·4DMF (2) have been synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses and single-crystal X-ray diffraction. X-ray diffraction studies show that complex 1 crystallizes in monoclinic, space group P21/c. The crystal of 2 belongs to a triclinic system with space group P1. Due to the hydrogen bonding interactions, anions and cations formed the mixed packing in complex 1 while the anions and cations formed segregated columns in 2. In addition, thermogravimetric analyses of the two complexes are also investigated.
