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2014 Volume 33 Issue 1
2014, 33(1): 7-18
Abstract:
With the improvement of high-tech and emergence of crossing and new fields, lanthanide-transition (Ln-M) heterometallic coordination polymers have attracted much attention of many researchers, which exhibit novel structures and unique properties with potential applications in the nonlinear optical materials, fluorescent materials, superconducting materials, magnetic materials, catalysis, bio-simulation, adsorption and separation, and so on. It is thus necessary to summarize Ln-M heterometallic coordination polymers. According to the transition metal ions, those coordination polymers are divided into six parts to explore the current applications and future developments.
With the improvement of high-tech and emergence of crossing and new fields, lanthanide-transition (Ln-M) heterometallic coordination polymers have attracted much attention of many researchers, which exhibit novel structures and unique properties with potential applications in the nonlinear optical materials, fluorescent materials, superconducting materials, magnetic materials, catalysis, bio-simulation, adsorption and separation, and so on. It is thus necessary to summarize Ln-M heterometallic coordination polymers. According to the transition metal ions, those coordination polymers are divided into six parts to explore the current applications and future developments.
2014, 33(1): 19-26
Abstract:
A novel anionic trinuclear linear copper(Ⅱ) complex {[Et3NH] [Cu0.5(CH3COO)-(TTA)3]}2 (1, TTA=2-thenoyltrifluoroacetonate) has been synthesized in a direct reaction involving copper(Ⅱ) acetate monohydrate, TTA and excess triethylamine base in dichloromethane solvent. Green colored X-ray quality crystals of 1 were grown from n-hexane solvent at room temperature. The data were collected at 100 K. Compound 1 crystallizes in the monoclinic P21/n space group (a=11.2141(8), b=19.0965(13), c=17.3680(14) Å, β=90.225(2)°, V=3719.3(5) Å3, Mr=1840.14, Dc=1.643 Mg/m3, F(000)=1866, μ=1.129 mm-1 and Z=2). The asymmetric unit of 1 contains two copper atoms, one of which lies on a crystallographic inversion center with 50% occupancy.
A novel anionic trinuclear linear copper(Ⅱ) complex {[Et3NH] [Cu0.5(CH3COO)-(TTA)3]}2 (1, TTA=2-thenoyltrifluoroacetonate) has been synthesized in a direct reaction involving copper(Ⅱ) acetate monohydrate, TTA and excess triethylamine base in dichloromethane solvent. Green colored X-ray quality crystals of 1 were grown from n-hexane solvent at room temperature. The data were collected at 100 K. Compound 1 crystallizes in the monoclinic P21/n space group (a=11.2141(8), b=19.0965(13), c=17.3680(14) Å, β=90.225(2)°, V=3719.3(5) Å3, Mr=1840.14, Dc=1.643 Mg/m3, F(000)=1866, μ=1.129 mm-1 and Z=2). The asymmetric unit of 1 contains two copper atoms, one of which lies on a crystallographic inversion center with 50% occupancy.
2014, 33(1): 27-32
Abstract:
A novel NiⅡ complex {[Ni(IBG)(μ-H2O)(H2O)2]·2H2O}n 1 (H2IBG=isophthaloyl-bisglycine) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, and thermogravimetric analysis. It crystallizes in monoclinic, space group P2/c with a=15.40(2), b=6.960(10), c=7.865(11) Å, β=90.32(3)°, V=843(2) Å3, Z=2, C12H18NiN2O11, Mr=424.99, Dc=1.675 g/cm3, F(000)=440, μ(MoKα)=1.214 mm-1, the final R=0.0514 and wR=0.1247 for 1078 observed reflections with I>2σ(I). In the structure, each NiⅡ center is situated in the center of a rather regular octahedron. Moreover, thermal stability has been studied and magnetic measurements show antiferromagnetic interactions for this complex.
A novel NiⅡ complex {[Ni(IBG)(μ-H2O)(H2O)2]·2H2O}n 1 (H2IBG=isophthaloyl-bisglycine) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, and thermogravimetric analysis. It crystallizes in monoclinic, space group P2/c with a=15.40(2), b=6.960(10), c=7.865(11) Å, β=90.32(3)°, V=843(2) Å3, Z=2, C12H18NiN2O11, Mr=424.99, Dc=1.675 g/cm3, F(000)=440, μ(MoKα)=1.214 mm-1, the final R=0.0514 and wR=0.1247 for 1078 observed reflections with I>2σ(I). In the structure, each NiⅡ center is situated in the center of a rather regular octahedron. Moreover, thermal stability has been studied and magnetic measurements show antiferromagnetic interactions for this complex.
2014, 33(1): 33-36
Abstract:
A new compound,[Zn(L)(1,4-chdc)]2·2H2O (1, 1,4-chdc=1,4-cyclohexanedicar-boxylate and L=11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. The crystal of 1 belongs to triclinic, space group P1 with a=9.4679(19), b=10.915(2), c=12.577(3) Å, α=77.22(3), β=74.73(3), γ=65.47(3)°, C52H39F2N8O10Zn2, Mr=1104.65, V=1131.4(4) Å3, Z=1, Dc=1.621 g/cm3,S=1.091, μ(MoKα)=1.143 mm-1, F(000)=565, R=0.0426 and wR=0.1171. In 1, two 1,4-chdc anions bridge two Zn(Ⅱ) atoms to form a dimer. The neighboring dimers are further extended by π-π stacking interactions to form a 2D supramolecular layer. The luminescent property of the compound has also been investigated.
A new compound,[Zn(L)(1,4-chdc)]2·2H2O (1, 1,4-chdc=1,4-cyclohexanedicar-boxylate and L=11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. The crystal of 1 belongs to triclinic, space group P1 with a=9.4679(19), b=10.915(2), c=12.577(3) Å, α=77.22(3), β=74.73(3), γ=65.47(3)°, C52H39F2N8O10Zn2, Mr=1104.65, V=1131.4(4) Å3, Z=1, Dc=1.621 g/cm3,S=1.091, μ(MoKα)=1.143 mm-1, F(000)=565, R=0.0426 and wR=0.1171. In 1, two 1,4-chdc anions bridge two Zn(Ⅱ) atoms to form a dimer. The neighboring dimers are further extended by π-π stacking interactions to form a 2D supramolecular layer. The luminescent property of the compound has also been investigated.
2014, 33(1): 37-42
Abstract:
The title compound 3-methyl-1-(4-methylphenyl)-4-(N-4-trifluoromethylphenyl) aminomethyl-5-(4-methoxyphenylthio)-1N-pyrazole has been synthesized via a four-step reaction and characterized by IR, 1H NMR, elemental analysis and X-ray crystallography. The compound crystallizes in monoclinic, space group P21/c with a=8.7170(15), b=18.355(3), c=15.292(3) Å, β=103.445(3)°, V=2379.7(7) Å3, Dc=1.350 g/cm3, Z=4, μ=0.184, F(000)=1008, and the final R=0.0491 and wR=0.1339 for 4160 observed reflections (I>2σ(I)). The results demonstrate that there is a face-to-face π-π stacking interaction between one benzene ring (C(19)~C(24)) and another (C(13)~C(18)) at a plane-plane distance of 3.3539 Å. The ring normal and vector between the ring centroids form an angle of 18.2° up to the centroid-to-centroid distance of 3.5273 Å. The crystal structure is stabilized by the intermolecular hydrogen bond of N(3)-H(3A)…N(2) (symmetry code:A-x+1,-y+1,-z). The preliminary biological test shows that the title compound has a moderate antifungal activity.
The title compound 3-methyl-1-(4-methylphenyl)-4-(N-4-trifluoromethylphenyl) aminomethyl-5-(4-methoxyphenylthio)-1N-pyrazole has been synthesized via a four-step reaction and characterized by IR, 1H NMR, elemental analysis and X-ray crystallography. The compound crystallizes in monoclinic, space group P21/c with a=8.7170(15), b=18.355(3), c=15.292(3) Å, β=103.445(3)°, V=2379.7(7) Å3, Dc=1.350 g/cm3, Z=4, μ=0.184, F(000)=1008, and the final R=0.0491 and wR=0.1339 for 4160 observed reflections (I>2σ(I)). The results demonstrate that there is a face-to-face π-π stacking interaction between one benzene ring (C(19)~C(24)) and another (C(13)~C(18)) at a plane-plane distance of 3.3539 Å. The ring normal and vector between the ring centroids form an angle of 18.2° up to the centroid-to-centroid distance of 3.5273 Å. The crystal structure is stabilized by the intermolecular hydrogen bond of N(3)-H(3A)…N(2) (symmetry code:A-x+1,-y+1,-z). The preliminary biological test shows that the title compound has a moderate antifungal activity.
2014, 33(1): 43-48
Abstract:
A new metal-organic framework, {[Cd(DPA)(OBA)]·(H2O)}n (1, DPA=4,4'-dipyri-dylamine, H2OBA=4,4'-oxybisbenzoic acid), has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Single-crystal X-ray analysis shows that it is a 3-D framework. Complex 1 crystallizes in monoclinic, space group C2/c with a=21.699(7), b=12.192(4), c=17.566(5) Å, β=105.254(5)°, V=4483.43 Å3, Z=8, Dc=1.653 g/cm3, μ=1.021 mm-1, F(000)=2240, the final R=0.0307, wR=0.0867 (I>2σ(I)). Complex 1 exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424·64}. Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400℃.
A new metal-organic framework, {[Cd(DPA)(OBA)]·(H2O)}n (1, DPA=4,4'-dipyri-dylamine, H2OBA=4,4'-oxybisbenzoic acid), has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Single-crystal X-ray analysis shows that it is a 3-D framework. Complex 1 crystallizes in monoclinic, space group C2/c with a=21.699(7), b=12.192(4), c=17.566(5) Å, β=105.254(5)°, V=4483.43 Å3, Z=8, Dc=1.653 g/cm3, μ=1.021 mm-1, F(000)=2240, the final R=0.0307, wR=0.0867 (I>2σ(I)). Complex 1 exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424·64}. Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400℃.
2014, 33(1): 49-56
Abstract:
All-atom molecular dynamics (MD) simulations and chemical shifts were used to study interactions and structures in the glycine-water system. Radial distribution functions and the hydrogen-bond network were applied in MD simulations. Aggregates in the aqueous glycine solution could be classified into different regions by analysis of the hydrogen-bonding network. Temperature-dependent NMR spectra and the viscosity of glycine in aqueous solutions were measured to compare with the results of MD simulations. The variation tendencies of the hydrogen atom chemical shifts and viscosity with concentration of glycine agree with the statistical results of hydrogen bonds in the MD simulations.
All-atom molecular dynamics (MD) simulations and chemical shifts were used to study interactions and structures in the glycine-water system. Radial distribution functions and the hydrogen-bond network were applied in MD simulations. Aggregates in the aqueous glycine solution could be classified into different regions by analysis of the hydrogen-bonding network. Temperature-dependent NMR spectra and the viscosity of glycine in aqueous solutions were measured to compare with the results of MD simulations. The variation tendencies of the hydrogen atom chemical shifts and viscosity with concentration of glycine agree with the statistical results of hydrogen bonds in the MD simulations.
2014, 33(1): 57-64
Abstract:
The ethyl coumarin-3-carboxylate (1) and its two derivatives, ethyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate (2) and ethyl 7-(3-methylbut-2-enyloxy)-2-oxo-2H-chromene-3-carboxylate(3), were synthesized, characterized and their UV-vis spectra and photoluminescence were investigated. Compound 2 crystallizes in the monoclinic system with space group C2/c, a=25.884(4), b=6.8365(11), c=13.816(2) Å, β=104.876(2)°, V=2362.9(7) Å3, Z=8, Dc=1.396 g/cm3, Mr=248.23, F(000)=1040 and μ=0.108 mm-1. Compound 3 crystallizes in the monoclinic system with space group P21/c, a=15.685(6), b=8.373(3), c=13.063(5) Å, β=111.862(6)°, V=1592.2(10) Å3, Z=4, Dc=1.261 g/cm3, Mr=302.31, F(000)=640 and μ=0.093 mm-1. Both the absorption and emission of the two derivatives were stronger than that of ethyl coumarin-3-carboxylate due to the larger conjugation of their electron donor group moiety at the 7-position. Under ultraviolet light excitation, the two derivatives exhibit strong blue-violet emission.
The ethyl coumarin-3-carboxylate (1) and its two derivatives, ethyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate (2) and ethyl 7-(3-methylbut-2-enyloxy)-2-oxo-2H-chromene-3-carboxylate(3), were synthesized, characterized and their UV-vis spectra and photoluminescence were investigated. Compound 2 crystallizes in the monoclinic system with space group C2/c, a=25.884(4), b=6.8365(11), c=13.816(2) Å, β=104.876(2)°, V=2362.9(7) Å3, Z=8, Dc=1.396 g/cm3, Mr=248.23, F(000)=1040 and μ=0.108 mm-1. Compound 3 crystallizes in the monoclinic system with space group P21/c, a=15.685(6), b=8.373(3), c=13.063(5) Å, β=111.862(6)°, V=1592.2(10) Å3, Z=4, Dc=1.261 g/cm3, Mr=302.31, F(000)=640 and μ=0.093 mm-1. Both the absorption and emission of the two derivatives were stronger than that of ethyl coumarin-3-carboxylate due to the larger conjugation of their electron donor group moiety at the 7-position. Under ultraviolet light excitation, the two derivatives exhibit strong blue-violet emission.
2014, 33(1): 65-70
Abstract:
The title compound stachyose (C24H42O21), a biologicaly active tetrasaccharide, was characterized by X-ray diffraction analysis. It crystallizes in the orthorhombic system, space group P21212 with C24H42O21, a=23.8760(3), b=12.71028(12), c=10.81279(11) Å, V=3281.36(6) Å3, Z=4, Dc=1.511 g/cm3, Mr=746.58, F(000)=1576, and μ=1.230 mm-1. The final R=0.0666 and wR=0.1797 for 6298 observed reflections (I>2σ(I)). The molecular crystal structure of stachyose shows absolute stereochemistry of β-D-fructofuranosyl α-D-galactopyranosyl-(1→6)-α-D-galactopyranosyl-(1→6)-α-D-glucopyranoside. The molecule is composed of two α-D-galactoses, one α-D-glucose, and one β-D-fructose and sequentially linked as α-Gal (1→6) α-Gal (1→6) α-Glc (1→2) β-Fru. The title compound is stacked into a 3D layer structure through hydrogen bonds. NMR spectra data are also assigned. In the crystal packing, X-ray analysis indicates that there are two intramolecular and eleven intermolecular hydrogen bonds in this compound.
The title compound stachyose (C24H42O21), a biologicaly active tetrasaccharide, was characterized by X-ray diffraction analysis. It crystallizes in the orthorhombic system, space group P21212 with C24H42O21, a=23.8760(3), b=12.71028(12), c=10.81279(11) Å, V=3281.36(6) Å3, Z=4, Dc=1.511 g/cm3, Mr=746.58, F(000)=1576, and μ=1.230 mm-1. The final R=0.0666 and wR=0.1797 for 6298 observed reflections (I>2σ(I)). The molecular crystal structure of stachyose shows absolute stereochemistry of β-D-fructofuranosyl α-D-galactopyranosyl-(1→6)-α-D-galactopyranosyl-(1→6)-α-D-glucopyranoside. The molecule is composed of two α-D-galactoses, one α-D-glucose, and one β-D-fructose and sequentially linked as α-Gal (1→6) α-Gal (1→6) α-Glc (1→2) β-Fru. The title compound is stacked into a 3D layer structure through hydrogen bonds. NMR spectra data are also assigned. In the crystal packing, X-ray analysis indicates that there are two intramolecular and eleven intermolecular hydrogen bonds in this compound.
2014, 33(1): 71-78
Abstract:
Density functional method was used to investigate the IR spectrum, heat of formation and thermal stability of a new energetic material bis(2,2-dinitropropyl) formal (BDNPF). The detonation velocity and pressure were evaluated by using the Kamlet-Jacobs equations based on the theoretical density and heat of formation. The bond dissociation energies for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that the C(1)-N(1) bond is predicted to be the trigger bond during pyrolysis. The crystal structure obtained by molecular mechanics belongs to the P21 space group, with the lattice parameters to be Z=2, a=11.5254, b=6.2168, c=9.5000 Å and ρ=1.66 g/cm3.
Density functional method was used to investigate the IR spectrum, heat of formation and thermal stability of a new energetic material bis(2,2-dinitropropyl) formal (BDNPF). The detonation velocity and pressure were evaluated by using the Kamlet-Jacobs equations based on the theoretical density and heat of formation. The bond dissociation energies for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that the C(1)-N(1) bond is predicted to be the trigger bond during pyrolysis. The crystal structure obtained by molecular mechanics belongs to the P21 space group, with the lattice parameters to be Z=2, a=11.5254, b=6.2168, c=9.5000 Å and ρ=1.66 g/cm3.
2014, 33(1): 79-84
Abstract:
Two substituted-3-phenylthiourea derivatives have been synthesized and characterized by elemental analysis, 1H NMR, MS and single-crystal X-ray diffraction. Structural stabilization of them followed by intramolecular as well as intermolecular H-bonds makes these molecules as perfect examples in molecular recognition with self-complementary donor and acceptor units within a single molecule. The antitumor activities of compounds 1 and 2 against breast adeno carcinoma cell line MCF-7 have been evaluated by MTT method. Docking simulations have also been performed to position compounds into the telomerase active sites so as to determine their probable binding models.
Two substituted-3-phenylthiourea derivatives have been synthesized and characterized by elemental analysis, 1H NMR, MS and single-crystal X-ray diffraction. Structural stabilization of them followed by intramolecular as well as intermolecular H-bonds makes these molecules as perfect examples in molecular recognition with self-complementary donor and acceptor units within a single molecule. The antitumor activities of compounds 1 and 2 against breast adeno carcinoma cell line MCF-7 have been evaluated by MTT method. Docking simulations have also been performed to position compounds into the telomerase active sites so as to determine their probable binding models.
2014, 33(1): 85-89
Abstract:
The title compound tianagliflozin triacetate 1 was synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic system (C27H31ClO8, Mr=518.97), space group P21 with a=5.3913(11), b=16.137(2), c=15.411(3) Å, β=94.15(3)°, V=1337.3(5) Å3, Z=2, Dc=1.289 g/cm3, F(000)=548, μ=0.190 mm-1, the final R=0.0374 and wR=0.0809 for 3981 observed reflections (I>2σ(I)). The structure of 1, triacetate of a highly potent SGLT2 inhibitor tianagliflozin, was unambiguously determined by single-crystal X-ray diffraction, which helped to confirm the desired β configuration at the anomeric center and the position where the deoxylation occurred. The two benzene rings in the lattice are basically orthogonal to each other. There are four intermolecular hydrogen bonds in the crystal, which helps to further stabilize the crystal.
The title compound tianagliflozin triacetate 1 was synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic system (C27H31ClO8, Mr=518.97), space group P21 with a=5.3913(11), b=16.137(2), c=15.411(3) Å, β=94.15(3)°, V=1337.3(5) Å3, Z=2, Dc=1.289 g/cm3, F(000)=548, μ=0.190 mm-1, the final R=0.0374 and wR=0.0809 for 3981 observed reflections (I>2σ(I)). The structure of 1, triacetate of a highly potent SGLT2 inhibitor tianagliflozin, was unambiguously determined by single-crystal X-ray diffraction, which helped to confirm the desired β configuration at the anomeric center and the position where the deoxylation occurred. The two benzene rings in the lattice are basically orthogonal to each other. There are four intermolecular hydrogen bonds in the crystal, which helps to further stabilize the crystal.
2014, 33(1): 90-96
Abstract:
The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (1) and 3-(4-fluoro-3-methylphenyl)quinoline (2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic acids. The title compounds were characterized by single-crystal X-ray diffraction, 1H NMR, 13C NMR, EI-MS, elemental analysis and IR. The crystals of 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (C17H9F6N, Mr=341.25) belongs to the monoclinic system, space group P21n, a=12.3072(13), b=4.9378(6), c=24.493(2) Å, V=1473.1(3) Å3, Z=4, Dc=1.539 Mg m-3, λ=0.71073 Å, μ=0.144 mm-1, F(000)=688, the final R=0.0715 and wR=0.1873 for 1875 observed reflections with I>2σ(I) and the crystal of 3-(4-fluoro-3-methylphenyl)quinoline (C16H12FN, Mr=237.27) belongs to the orthorhombic system, space group Pca21, a=23.794(2), b=3.9094(3), c=25.669(2) Å, V=2387.7(4) Å3, Z=8, Dc=1.320 Mg m-3, λ=0.71073 Å, μ=0.088 mm-1, F(000)=992, the final R=0.0534 and wR=0.1188 for 2270 observed reflections with I>2σ(I).
The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (1) and 3-(4-fluoro-3-methylphenyl)quinoline (2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic acids. The title compounds were characterized by single-crystal X-ray diffraction, 1H NMR, 13C NMR, EI-MS, elemental analysis and IR. The crystals of 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (C17H9F6N, Mr=341.25) belongs to the monoclinic system, space group P21n, a=12.3072(13), b=4.9378(6), c=24.493(2) Å, V=1473.1(3) Å3, Z=4, Dc=1.539 Mg m-3, λ=0.71073 Å, μ=0.144 mm-1, F(000)=688, the final R=0.0715 and wR=0.1873 for 1875 observed reflections with I>2σ(I) and the crystal of 3-(4-fluoro-3-methylphenyl)quinoline (C16H12FN, Mr=237.27) belongs to the orthorhombic system, space group Pca21, a=23.794(2), b=3.9094(3), c=25.669(2) Å, V=2387.7(4) Å3, Z=8, Dc=1.320 Mg m-3, λ=0.71073 Å, μ=0.088 mm-1, F(000)=992, the final R=0.0534 and wR=0.1188 for 2270 observed reflections with I>2σ(I).
2014, 33(1): 97-103
Abstract:
Two new Cu(Ⅱ) coordination polymers,[Cu(FDA)(BPY)(H2O)]n (1) and {[Cu(FDA)(BPY)(H2O)]·2H2O}n (2) (H2FDA=2,5-furandicarboxylic acid, BPY=2,2'-bipyridine), have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a=7.5915(15), b=8.4050(17), c=24.204(6) Å, β=99.05(3)°, V=1525.1(6) Å3, Dc=1.706 g/cm3, C16H12CuN2O6, Mr=391.82, F(000)=796, μ(MoKα)=1.470 mm-1, Z=4, R=0.0633 and wR=0.1059 for 2389 observed reflections (I>2σ(I)), R=0.0738, and wR=0.1098 for all data. Complex 2 belongs to triclinic space group P1 with a=8.8660(18), b=8.9112(18), c=12.525(3) Å, α=88.41(3), β=69.38(3), γ=66.95(3)°, V=845.2(3) Å3, Dc=1.681 g/cm3, C16H16CuN2O8, Mr=427.85, F(000)=438, μ(MoKα)=1.342 mm-1, Z=2, R=0.0290 and wR=0.0690 for 2767 observed reflections (I>2σ(I)), R=0.0329 and wR=0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.
Two new Cu(Ⅱ) coordination polymers,[Cu(FDA)(BPY)(H2O)]n (1) and {[Cu(FDA)(BPY)(H2O)]·2H2O}n (2) (H2FDA=2,5-furandicarboxylic acid, BPY=2,2'-bipyridine), have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a=7.5915(15), b=8.4050(17), c=24.204(6) Å, β=99.05(3)°, V=1525.1(6) Å3, Dc=1.706 g/cm3, C16H12CuN2O6, Mr=391.82, F(000)=796, μ(MoKα)=1.470 mm-1, Z=4, R=0.0633 and wR=0.1059 for 2389 observed reflections (I>2σ(I)), R=0.0738, and wR=0.1098 for all data. Complex 2 belongs to triclinic space group P1 with a=8.8660(18), b=8.9112(18), c=12.525(3) Å, α=88.41(3), β=69.38(3), γ=66.95(3)°, V=845.2(3) Å3, Dc=1.681 g/cm3, C16H16CuN2O8, Mr=427.85, F(000)=438, μ(MoKα)=1.342 mm-1, Z=2, R=0.0290 and wR=0.0690 for 2767 observed reflections (I>2σ(I)), R=0.0329 and wR=0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.
2014, 33(1): 104-114
Abstract:
The novel linear, circular, hooped, and helical molecules based on oligo[8]thio-phene were theoretically studied for the applications of charge transfer devices. To investigate the influence of topology for oligo[8]thiophene derivatives, the geometry structures, frontier molecular orbital (FMO) energies, charge transport properties, and stability property were predicted by density functional theory methods. The calculated results reported herein show that the oligo[8]thiophene derivative with linear structure has smaller energy gap, and fused oligo[8]thiophene derivative with circular structure has the smallest reorganization energy among the designed molecules. We have also studied the stability properties of the designed molecules, and oligo[8]thiophene derivatives are more stable than the fused oligo[8]thiophene derivatives.
The novel linear, circular, hooped, and helical molecules based on oligo[8]thio-phene were theoretically studied for the applications of charge transfer devices. To investigate the influence of topology for oligo[8]thiophene derivatives, the geometry structures, frontier molecular orbital (FMO) energies, charge transport properties, and stability property were predicted by density functional theory methods. The calculated results reported herein show that the oligo[8]thiophene derivative with linear structure has smaller energy gap, and fused oligo[8]thiophene derivative with circular structure has the smallest reorganization energy among the designed molecules. We have also studied the stability properties of the designed molecules, and oligo[8]thiophene derivatives are more stable than the fused oligo[8]thiophene derivatives.
2014, 33(1): 115-121
Abstract:
The title complex N,N'-bis(2-benzoyl-3-oxobutane)-trans-1,2-diaminocyclo-hexane-palladium (C28H28N2PdO4) has been synthesized by the reaction of N,N'-bis(2-benzoyl-3-oxobutane)-trans-1,2-diamino-cyclohexane with PdCl2, and characterized by elemental analysis, IR spectrum, WAXD and TG. The spatial structures of the complex have been confirmed by single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group C2/c with a=29.763(6), b=10.320(2), c=18.921(4) Å, β=102.75(3)°, V=5668(2) Å3, C28H28N2PdO4·CH3OH, Mr=594.97, Z=8, Dc=1.394 g/cm3, μ(MoKα)=0.694 mm-1, F(000)=2448, T=293(2) K, R=0.0572 and wR=0.1347 (I>2σ(I)). The compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the palladium complex showed excellent catalytic activity up to 9.97×106g of PNB (mol of Pd)-1 h-1 with high monomer conversion using methylaluminoxane (MAO) as a cocatalyst.
The title complex N,N'-bis(2-benzoyl-3-oxobutane)-trans-1,2-diaminocyclo-hexane-palladium (C28H28N2PdO4) has been synthesized by the reaction of N,N'-bis(2-benzoyl-3-oxobutane)-trans-1,2-diamino-cyclohexane with PdCl2, and characterized by elemental analysis, IR spectrum, WAXD and TG. The spatial structures of the complex have been confirmed by single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group C2/c with a=29.763(6), b=10.320(2), c=18.921(4) Å, β=102.75(3)°, V=5668(2) Å3, C28H28N2PdO4·CH3OH, Mr=594.97, Z=8, Dc=1.394 g/cm3, μ(MoKα)=0.694 mm-1, F(000)=2448, T=293(2) K, R=0.0572 and wR=0.1347 (I>2σ(I)). The compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the palladium complex showed excellent catalytic activity up to 9.97×106g of PNB (mol of Pd)-1 h-1 with high monomer conversion using methylaluminoxane (MAO) as a cocatalyst.
2014, 33(1): 122-134
Abstract:
A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes CnH2n (n=3~7) is carried out. For the Ni+CnH2n (n=3, 4) reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n (n=5~7). The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized. It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n (n=3~7).
A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes CnH2n (n=3~7) is carried out. For the Ni+CnH2n (n=3, 4) reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n (n=5~7). The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized. It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n (n=3~7).
2014, 33(1): 135-147
Abstract:
The structures of the complexes formed between N-methylol ethanone (model molecule of ceramide) and azacyclopentane-2-one (the model molecule of azone) have been fully optimized at the B3LYP/6-311++G** level. The intermolecular hydrogen bonding interaction energies have been calculated by using the B3LYP/6-311++G**, B3LYP/6-311++G(2df,2p), MP2(full)/6-311++G** and MP2(full)/6-311++G(2df,2p) methods, respectively. The results show that strong O-H…O=C, N-H…O=C and C-H…O=C hydrogen bonds could exist between azacyclopentane-2-one and N-methylol ethanone. The formation of the complexes might change the conformation of ceramide molecule and thus cause better percutaneous permeation for the drugs. This is perhaps the origin of the permeation enhances the activity of azone for medicament, as is in accordance with the experimental results. The hydrogen-bonding interactions follow the order of (a) >(c) >(b) >(d) >(g)≈(e)≈(i) >(h) >(f). The analyses of frequency, NBO, AIM and electron density shift are used to further reveal the nature of the complex formation. In the range of 263.0~328.0 K, the complex is formed via an exothermic reaction, and the solvent with lower temperature and dielectric constant is favorable to this process.
The structures of the complexes formed between N-methylol ethanone (model molecule of ceramide) and azacyclopentane-2-one (the model molecule of azone) have been fully optimized at the B3LYP/6-311++G** level. The intermolecular hydrogen bonding interaction energies have been calculated by using the B3LYP/6-311++G**, B3LYP/6-311++G(2df,2p), MP2(full)/6-311++G** and MP2(full)/6-311++G(2df,2p) methods, respectively. The results show that strong O-H…O=C, N-H…O=C and C-H…O=C hydrogen bonds could exist between azacyclopentane-2-one and N-methylol ethanone. The formation of the complexes might change the conformation of ceramide molecule and thus cause better percutaneous permeation for the drugs. This is perhaps the origin of the permeation enhances the activity of azone for medicament, as is in accordance with the experimental results. The hydrogen-bonding interactions follow the order of (a) >(c) >(b) >(d) >(g)≈(e)≈(i) >(h) >(f). The analyses of frequency, NBO, AIM and electron density shift are used to further reveal the nature of the complex formation. In the range of 263.0~328.0 K, the complex is formed via an exothermic reaction, and the solvent with lower temperature and dielectric constant is favorable to this process.
2014, 33(1): 148-164
Abstract:
The space groups of 244 crystal structures originally reported as P-1 are revised to space groups of higher symmetry. The largest number involves revisions to P21/c and C2/c.
The space groups of 244 crystal structures originally reported as P-1 are revised to space groups of higher symmetry. The largest number involves revisions to P21/c and C2/c.
