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2014 Volume 33 Issue 5
2014, 33(5): 661-668
Abstract:
The geometric configurations and electronic structures of AlSn±(n=1~10) clusters were studied by the B3LYP (DFT) method at the 6-311G** level. The changing rules of the ground state structure features, charge transfer and bonding characteristics of the aluminum-sulfur doped clusters were discussed in detail. The ground states of AlSn±(n>2) are all AlcoreSshell planar or solid double ring structures formed by inserting one Al atom to the Sm and Sn-m (m<n) rings at the same time. Their molecular orbitals are mainly composed of Al s- and p-states mixed with S p-states. Finally, the stabilities of AlSn±clusters have been obtained by analyzing the energy of the ground state structures.
The geometric configurations and electronic structures of AlSn±(n=1~10) clusters were studied by the B3LYP (DFT) method at the 6-311G** level. The changing rules of the ground state structure features, charge transfer and bonding characteristics of the aluminum-sulfur doped clusters were discussed in detail. The ground states of AlSn±(n>2) are all AlcoreSshell planar or solid double ring structures formed by inserting one Al atom to the Sm and Sn-m (m<n) rings at the same time. Their molecular orbitals are mainly composed of Al s- and p-states mixed with S p-states. Finally, the stabilities of AlSn±clusters have been obtained by analyzing the energy of the ground state structures.
2014, 33(5): 669-675
Abstract:
In this paper, proton transfer mechanism of alanine induced by Zn2+ was investigated by the CCSD/6-31++G**//B3LYP/6-31++G** method. Six neutral complexes and one amphoteric complex were optimized, among which the amphoteric complex was the most stable with binding energy of 201.92 kcal·mol-1. In addition, the rotation of intramolecular single bond leads to the neutral configuration conversion, in which the rotation energy barriers of C-C single bonds are lower than 10.51 kcal·mol-1, and those of C-O single bonds range among 9.53~17.50 kcal·mol-1. On the other hand, the proton transfers among the carboxylic oxygen atoms can also result in the neutral configuration conversion, whose energy barriers of forward/back reaction are 53.90 and 32.46 kcal·mol-1, respectively. In detail, the proton transfers from carboxylic group to amino lead to their configuration conversion from neutral to amphoteric. Furthermore, under the catalysis of Zn2+, there was no energy barrier in this reaction. The conversion route from the most stable neutral configuration Ⅱ to the most stable amphoteric configuration Ⅰ was: Ⅱ→Ⅱ-Ⅲ→Ⅲ→Ⅲ-Ⅵ→Ⅵ→Ⅴ-Ⅵ→Ⅴ→Ⅰ-Ⅴ→Ⅰ, with the energy barrier to be 64.64 kcal·mol-1.
In this paper, proton transfer mechanism of alanine induced by Zn2+ was investigated by the CCSD/6-31++G**//B3LYP/6-31++G** method. Six neutral complexes and one amphoteric complex were optimized, among which the amphoteric complex was the most stable with binding energy of 201.92 kcal·mol-1. In addition, the rotation of intramolecular single bond leads to the neutral configuration conversion, in which the rotation energy barriers of C-C single bonds are lower than 10.51 kcal·mol-1, and those of C-O single bonds range among 9.53~17.50 kcal·mol-1. On the other hand, the proton transfers among the carboxylic oxygen atoms can also result in the neutral configuration conversion, whose energy barriers of forward/back reaction are 53.90 and 32.46 kcal·mol-1, respectively. In detail, the proton transfers from carboxylic group to amino lead to their configuration conversion from neutral to amphoteric. Furthermore, under the catalysis of Zn2+, there was no energy barrier in this reaction. The conversion route from the most stable neutral configuration Ⅱ to the most stable amphoteric configuration Ⅰ was: Ⅱ→Ⅱ-Ⅲ→Ⅲ→Ⅲ-Ⅵ→Ⅵ→Ⅴ-Ⅵ→Ⅴ→Ⅰ-Ⅴ→Ⅰ, with the energy barrier to be 64.64 kcal·mol-1.
2014, 33(5): 676-686
Abstract:
Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquinolin-7-one (1) and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one (2) have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory (DFT) calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G** level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G** level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.
Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquinolin-7-one (1) and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one (2) have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory (DFT) calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G** level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G** level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.
2014, 33(5): 687-694
Abstract:
Two new complexes, [Cu(DMB)2(NAA)2] (1) and [Co(DMB)2(NAA)2] (2) (DMB=5,6-dimethylbenzimidazole, HNNA=1-naphthylacetic acid), were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA, PXRD and single-crystal X-ray diffraction analysis. The coordination geometry of the metal centers is a perfect square plane for 1 and a distorted tetrahedron for 2. In compound 1, the mononuclear units are linked by N-H…O hydrogen bonds to form a 1D chain structure, while mononuclear motifs of 2 are extended via N-H…O hydrogen bonding and π-π stacking interactions into a 2D supramolecular layer. The remarkable catalytic properties of the two complexes for the degradation of Congo red dye have been found.
Two new complexes, [Cu(DMB)2(NAA)2] (1) and [Co(DMB)2(NAA)2] (2) (DMB=5,6-dimethylbenzimidazole, HNNA=1-naphthylacetic acid), were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA, PXRD and single-crystal X-ray diffraction analysis. The coordination geometry of the metal centers is a perfect square plane for 1 and a distorted tetrahedron for 2. In compound 1, the mononuclear units are linked by N-H…O hydrogen bonds to form a 1D chain structure, while mononuclear motifs of 2 are extended via N-H…O hydrogen bonding and π-π stacking interactions into a 2D supramolecular layer. The remarkable catalytic properties of the two complexes for the degradation of Congo red dye have been found.
2014, 33(5): 695-700
Abstract:
A two-dimensional (2D) 44 topological ZnⅡ coordination polymer {[Zn2Cl2(L)(4bpy)2]}∞ (H2L=anthracene-9,10-dicarboxylic acid, 4bpy=4,4'-bipyridine) based on binuclear [Zn2Cl2] nodes has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction analysis. Moreover, the luminescent properties of the corresponding compound have been briefly investigated.
A two-dimensional (2D) 44 topological ZnⅡ coordination polymer {[Zn2Cl2(L)(4bpy)2]}∞ (H2L=anthracene-9,10-dicarboxylic acid, 4bpy=4,4'-bipyridine) based on binuclear [Zn2Cl2] nodes has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction analysis. Moreover, the luminescent properties of the corresponding compound have been briefly investigated.
2014, 33(5): 701-706
Abstract:
A new nickel coordination polymer {[Ni(dpa)(bpe)(H2O)]2}n (1) has been hydrothermally synthesized, and structurally characterized by UV spectroscopy, elemental analyses and single-crystal X-ray diffraction (H2dpa=3-(4-hydroxypyridinium-1-yl) phthalic acid, bpe=μ-1,2-di(4-pyridyl) ethylene). It crystallizes in the triclinic system, space group P1 with a=8.779(2), b=10.909(3), c=12.739(3)Å, α=72.45(2), β=75.13(2), γ=86.47(2)°, V=1124.1(5)Å3, Z=2, Mr=516.14, Dc=1.525 g/cm3, μ=0.912 mm-1,Rint=0.0532, F(000)=532, the final R=0.0523 and wR=0.1089 for 3949 observed reflections (I>2σ(I)). The coordination around the Ni center is a distorted octahedron coordination geometry involving two protonated H2dpa ligands, two bpe ligands, and one coordinated H2O molecule. The dpa2- anion, as a bridging ligand, connects two Ni centers to form binuclear units, which are linked together by the bpe ligands to form two-dimensional layers, and the interlayer hydrogen bonding further extends the 2D sheet into a 3D supramolecular framework.
A new nickel coordination polymer {[Ni(dpa)(bpe)(H2O)]2}n (1) has been hydrothermally synthesized, and structurally characterized by UV spectroscopy, elemental analyses and single-crystal X-ray diffraction (H2dpa=3-(4-hydroxypyridinium-1-yl) phthalic acid, bpe=μ-1,2-di(4-pyridyl) ethylene). It crystallizes in the triclinic system, space group P1 with a=8.779(2), b=10.909(3), c=12.739(3)Å, α=72.45(2), β=75.13(2), γ=86.47(2)°, V=1124.1(5)Å3, Z=2, Mr=516.14, Dc=1.525 g/cm3, μ=0.912 mm-1,Rint=0.0532, F(000)=532, the final R=0.0523 and wR=0.1089 for 3949 observed reflections (I>2σ(I)). The coordination around the Ni center is a distorted octahedron coordination geometry involving two protonated H2dpa ligands, two bpe ligands, and one coordinated H2O molecule. The dpa2- anion, as a bridging ligand, connects two Ni centers to form binuclear units, which are linked together by the bpe ligands to form two-dimensional layers, and the interlayer hydrogen bonding further extends the 2D sheet into a 3D supramolecular framework.
2014, 33(5): 707-712
Abstract:
The reactions of chiral four-coordinated nickel(Ⅱ) complex [Ni(RR-L)](ClO4)2/[Ni(SS-L)](ClO4)2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni(RR-L)(β-d-HPhe)](ClO4)2 (1) and [Ni(SS-L)(β-l-HPhe)](ClO4)2 (2), respectively (L=5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe=phenylalanine). Single-crystal X-ray diffraction analyses revealed that the nickel(Ⅱ) atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni(RR-L)(β-d-HPhe)]2+ and [Ni(SS-L)(β-l-HPhe)]2+ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.
The reactions of chiral four-coordinated nickel(Ⅱ) complex [Ni(RR-L)](ClO4)2/[Ni(SS-L)](ClO4)2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni(RR-L)(β-d-HPhe)](ClO4)2 (1) and [Ni(SS-L)(β-l-HPhe)](ClO4)2 (2), respectively (L=5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe=phenylalanine). Single-crystal X-ray diffraction analyses revealed that the nickel(Ⅱ) atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni(RR-L)(β-d-HPhe)]2+ and [Ni(SS-L)(β-l-HPhe)]2+ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.
2014, 33(5): 713-720
Abstract:
The self-assembly of 1,10-phenanthroline (phen) and 1,3-benzenedicarboxylic acid (H2bdc) with Pb(NO3)2 under solvothermal conditions in N,N-dimethylacetamide (DMA) gives rise to a one-dimensional chain coordination polymer, [Pb(phen)(bdc)] (1), which was characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group P1 with a=7.5595(6), b=9.8199(8), c=13.1663(11)Å, α=69.7590(10), β=80.6000(10), γ=71.3180(10)°, Z=2, C20H12N2O4Pb, Mr=551.51, Dc=2.112 g/cm3, F(000)=520 and μ=9.757 mm-1. The final R=0.0304 and wR=0.0763 for 3427 observed reflections with I>2σ(I) and R=0.0365 and wR=0.0894 for all data. The structure contains one crystallographic unique Pb(Ⅱ) atom, one phen molecule chelating with a Pb(Ⅱ) atom, and one bdc2- anion, acting as a bidentate bridging ligand linking the Pb(Ⅱ) atoms to form a one-dimensional structure. The two-dimensional layer and three-dimensional stacking structures are formed by C-H…O hydrogen bonding interactions. The thermal stable and fluorescent properties of 1 were investigated. PbO micro-crystal particles are produced by calcination of powder sample of complex 1. The obtained PbO is characterized and observed by XRD and SEM analyses.
The self-assembly of 1,10-phenanthroline (phen) and 1,3-benzenedicarboxylic acid (H2bdc) with Pb(NO3)2 under solvothermal conditions in N,N-dimethylacetamide (DMA) gives rise to a one-dimensional chain coordination polymer, [Pb(phen)(bdc)] (1), which was characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group P1 with a=7.5595(6), b=9.8199(8), c=13.1663(11)Å, α=69.7590(10), β=80.6000(10), γ=71.3180(10)°, Z=2, C20H12N2O4Pb, Mr=551.51, Dc=2.112 g/cm3, F(000)=520 and μ=9.757 mm-1. The final R=0.0304 and wR=0.0763 for 3427 observed reflections with I>2σ(I) and R=0.0365 and wR=0.0894 for all data. The structure contains one crystallographic unique Pb(Ⅱ) atom, one phen molecule chelating with a Pb(Ⅱ) atom, and one bdc2- anion, acting as a bidentate bridging ligand linking the Pb(Ⅱ) atoms to form a one-dimensional structure. The two-dimensional layer and three-dimensional stacking structures are formed by C-H…O hydrogen bonding interactions. The thermal stable and fluorescent properties of 1 were investigated. PbO micro-crystal particles are produced by calcination of powder sample of complex 1. The obtained PbO is characterized and observed by XRD and SEM analyses.
2014, 33(5): 721-728
Abstract:
Hydrothermal reactions of 5-(pyridin-2-yl-methyl)aminoisophthalic acid (H2paip) with Mn(OAc)2·4H2O and Cu(NO3)2·3H2O produced two 2D complexes, [Mn(paip)]n·nH2O (1) and [Cu(paip)(H2O)]n (2). In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn(Ⅱ) into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu(Ⅱ) into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.
Hydrothermal reactions of 5-(pyridin-2-yl-methyl)aminoisophthalic acid (H2paip) with Mn(OAc)2·4H2O and Cu(NO3)2·3H2O produced two 2D complexes, [Mn(paip)]n·nH2O (1) and [Cu(paip)(H2O)]n (2). In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn(Ⅱ) into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu(Ⅱ) into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.
2014, 33(5): 729-734
Abstract:
A new 3D Ag(Ⅰ) coordination polymer, [Ag8(btc)2(bpp)2]n (1, H4btc=biphenyl-2,2',4,4'-tetracarboxylic acid, bpp=1,2-bis(4-pyridyl)propane), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. Complex 1 crystallizes in the triclinic system, space group P1 with a=13.4899(8), b=13.4928(8), c=16.4575(10)Å, α=102.7640(10), β=108.8100(10), γ=101.4940(10)°, V=2644.1(3)Å3, Z=2, Dc=2.401 Mg·m-3, μ=2.978 mm-1, F(000)=1840, the final R=0.0481 and wR=0.0955 for 6794 observed reflections with I>2σ(I). Complex 1 features a 3D framework formed by Ag (I)-carboxylate chains containing [Ag16(COO)16] secondary building block. Furthermore, thermal stability and electrochemical property of 1 are also investigated in detail.
A new 3D Ag(Ⅰ) coordination polymer, [Ag8(btc)2(bpp)2]n (1, H4btc=biphenyl-2,2',4,4'-tetracarboxylic acid, bpp=1,2-bis(4-pyridyl)propane), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. Complex 1 crystallizes in the triclinic system, space group P1 with a=13.4899(8), b=13.4928(8), c=16.4575(10)Å, α=102.7640(10), β=108.8100(10), γ=101.4940(10)°, V=2644.1(3)Å3, Z=2, Dc=2.401 Mg·m-3, μ=2.978 mm-1, F(000)=1840, the final R=0.0481 and wR=0.0955 for 6794 observed reflections with I>2σ(I). Complex 1 features a 3D framework formed by Ag (I)-carboxylate chains containing [Ag16(COO)16] secondary building block. Furthermore, thermal stability and electrochemical property of 1 are also investigated in detail.
Structure and Magnetic Properties of a Bipyridine-bridged One-dimensional Ni(Ⅱ) Coordination Polymer
2014, 33(5): 735-740
Abstract:
A polymer, [NiL(bipy)·2H2O]n (1, bipy=4,4'-bipyridine), has been acquired by the reaction of Ni(OAc)2·4H2O with N,N'-bis(2-hydroxyl-5-fluorobenzyl)-2-hydrxylpropane diimine in the presence of 4,4'-bipyridine. X-ray crystallographic analysis shows that it is comprised of a mononuclear Ni(Ⅱ) complex [NiL] linked by 4,4'-bipyridine. Its crystal crystallizes in the orthorhombic system, space group C2/c with a=22.595(3), b=18.395(2), c=15.434(2)Å, V=6155(1)Å3, Dc=1.259 g/cm-3, Z=8, Mr=583.23, F(000)=2416.0, μ(MoKa)=0.681 mm-1, S=1.049, R=0.0512 and wR=0.1108 for 6032 observed reflections (I>2σ(I)). There are water hexamers in the complex. A weak overall ferromagnetic behavior has been evaluated by Curie-Weiss rule and by the formula of alternating ferro-ferromagnetic coupling in one-dimensional Ni(Ⅱ) chain, which gives g=2.005(1) and J1=0.31(3) cm-1.
A polymer, [NiL(bipy)·2H2O]n (1, bipy=4,4'-bipyridine), has been acquired by the reaction of Ni(OAc)2·4H2O with N,N'-bis(2-hydroxyl-5-fluorobenzyl)-2-hydrxylpropane diimine in the presence of 4,4'-bipyridine. X-ray crystallographic analysis shows that it is comprised of a mononuclear Ni(Ⅱ) complex [NiL] linked by 4,4'-bipyridine. Its crystal crystallizes in the orthorhombic system, space group C2/c with a=22.595(3), b=18.395(2), c=15.434(2)Å, V=6155(1)Å3, Dc=1.259 g/cm-3, Z=8, Mr=583.23, F(000)=2416.0, μ(MoKa)=0.681 mm-1, S=1.049, R=0.0512 and wR=0.1108 for 6032 observed reflections (I>2σ(I)). There are water hexamers in the complex. A weak overall ferromagnetic behavior has been evaluated by Curie-Weiss rule and by the formula of alternating ferro-ferromagnetic coupling in one-dimensional Ni(Ⅱ) chain, which gives g=2.005(1) and J1=0.31(3) cm-1.
2014, 33(5): 741-745
Abstract:
The synthesis, structure and luminescent property of a tetranuclear gold(I) complex with doubly bridging diethyldithiocarbamate (Et2dtc) and 1,1-bis(diphenylphosphino)ethene ((Ph2P)2C=CH2) are described. The complex crystallizes in monoclinic space group C2/c with a=26.785(7), b=25.654(6), c=12.277(3)Å, β=106.879(5)°, V=8073(4)Å3, Z=8, C31H32Au2F6NO3P2S2Sb, Mr=1222.32, Dc=2.011 g/cm3, F(000)=4592,Rint=0.0529, T=293(2) K, μ=8.157 mm-1, the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I>2σ(I). The intramolecular and intermolecular Au…Au distances are 2.8670(9) and 3.2367(9)Å, respectively. Weak emission appears at 517 nm at room temperature in the solid state.
The synthesis, structure and luminescent property of a tetranuclear gold(I) complex with doubly bridging diethyldithiocarbamate (Et2dtc) and 1,1-bis(diphenylphosphino)ethene ((Ph2P)2C=CH2) are described. The complex crystallizes in monoclinic space group C2/c with a=26.785(7), b=25.654(6), c=12.277(3)Å, β=106.879(5)°, V=8073(4)Å3, Z=8, C31H32Au2F6NO3P2S2Sb, Mr=1222.32, Dc=2.011 g/cm3, F(000)=4592,Rint=0.0529, T=293(2) K, μ=8.157 mm-1, the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I>2σ(I). The intramolecular and intermolecular Au…Au distances are 2.8670(9) and 3.2367(9)Å, respectively. Weak emission appears at 517 nm at room temperature in the solid state.
2014, 33(5): 746-752
Abstract:
The title complex [Sr3(pda)2(Hpda)2(H2O)2]n·2nH2O (H2pda=pyridine-2,6-dicarboxylic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a=10.3795(8), b=9.2225(7), c=18.5726(14)Å, β=104.377(2)°, V=1722.2(2)Å3, C28H22N4O20Sr3, Mr=997.36, Z=2, Dc=1.923 g/cm3, μ=4.722 mm-1, F(000)=984, the final R=0.0269 and wR=0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.
The title complex [Sr3(pda)2(Hpda)2(H2O)2]n·2nH2O (H2pda=pyridine-2,6-dicarboxylic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a=10.3795(8), b=9.2225(7), c=18.5726(14)Å, β=104.377(2)°, V=1722.2(2)Å3, C28H22N4O20Sr3, Mr=997.36, Z=2, Dc=1.923 g/cm3, μ=4.722 mm-1, F(000)=984, the final R=0.0269 and wR=0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.
2014, 33(5): 753-756
Abstract:
The title compound of Cu(C14H9O3)2(C5H5N)2(C2H5OH)2 (1) was synthesized via the hydrothermal reaction of CuCl2·2H2O and 9-hydroxy-fluorene-9-carboxylic acid (HHF) with pyridine, and characterized by elemental analysis and infrared spectra. The crystal belongs to triclinic, space group P1 with a=8.8302(12), b=10.1625(14), c=12.2708(17)Å, α=86.207(2), β=69.562(2), γ=64.932(2)°, V=930.3(2)Å3, Z=1, Mr=764.30, Dc=1.364 g/cm3, F(000)=399, S=1.059 and μ(MoKα)=0.644 mm-1. The final R=0.0459 and wR=0.1274 for 3414 observed reflections with I>2σ(I). The copper atom is six-coordinated by two oxygen atoms from two different 9-hydroxy-fluorene-9-carboxylate ligands, two pyridine nitrogen atoms and two ethanol oxygen atoms, forming a distorted octahedral coordination geometry. The extensive O-H…O hydrogen bonding connects the molecules to form a one-dimensional chain structure. Between adjacent one-dimensional chains, a two-dimensional layered structure was formed by fluorene ring π-π packing interaction. Between the layers, a three-dimensional structure was formed through the π-π packing interaction of the pyridine ring. Moreover, the thermal stability and photoluminescent property of the complex has been investigated.
The title compound of Cu(C14H9O3)2(C5H5N)2(C2H5OH)2 (1) was synthesized via the hydrothermal reaction of CuCl2·2H2O and 9-hydroxy-fluorene-9-carboxylic acid (HHF) with pyridine, and characterized by elemental analysis and infrared spectra. The crystal belongs to triclinic, space group P1 with a=8.8302(12), b=10.1625(14), c=12.2708(17)Å, α=86.207(2), β=69.562(2), γ=64.932(2)°, V=930.3(2)Å3, Z=1, Mr=764.30, Dc=1.364 g/cm3, F(000)=399, S=1.059 and μ(MoKα)=0.644 mm-1. The final R=0.0459 and wR=0.1274 for 3414 observed reflections with I>2σ(I). The copper atom is six-coordinated by two oxygen atoms from two different 9-hydroxy-fluorene-9-carboxylate ligands, two pyridine nitrogen atoms and two ethanol oxygen atoms, forming a distorted octahedral coordination geometry. The extensive O-H…O hydrogen bonding connects the molecules to form a one-dimensional chain structure. Between adjacent one-dimensional chains, a two-dimensional layered structure was formed by fluorene ring π-π packing interaction. Between the layers, a three-dimensional structure was formed through the π-π packing interaction of the pyridine ring. Moreover, the thermal stability and photoluminescent property of the complex has been investigated.
2014, 33(5): 757-763
Abstract:
A new three-dimensional (3D) coordination polymer, [Cd(L)2H2O]n·5nH2O 1 with 4-[(3-pyridyl)methylamino]benzoate acid (HL), has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a=20.7937(16), c=13.515(2), V=5843.5(11)Å3, C26H34CdN4O10, Mr=674.97, Dc=1.534 g/cm3, μ(MoKα)=0.808 mm-1, F(000)=2768, Z=8, the final R=0.0276 and wR=0.0691 for 5323 observed reflections (I>2σ(I)). The result of thermal analysis shows that 1 is stable under 290℃ . Moreover, it exhibits blue photoluminescence at room temperature.
A new three-dimensional (3D) coordination polymer, [Cd(L)2H2O]n·5nH2O 1 with 4-[(3-pyridyl)methylamino]benzoate acid (HL), has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a=20.7937(16), c=13.515(2), V=5843.5(11)Å3, C26H34CdN4O10, Mr=674.97, Dc=1.534 g/cm3, μ(MoKα)=0.808 mm-1, F(000)=2768, Z=8, the final R=0.0276 and wR=0.0691 for 5323 observed reflections (I>2σ(I)). The result of thermal analysis shows that 1 is stable under 290℃ . Moreover, it exhibits blue photoluminescence at room temperature.
2014, 33(5): 764-770
Abstract:
Two novel compounds, {[Cd(nbdc)(bpp)(H2O)]·H2O}n 1 and {[Cd(nbdc)(dpds)(H2O)]·H2O}n 2 (H2nbdc=4-nitro-1,2-benzenedicarboxylic acid, bpp=1,3-bis(4-pyridyl)propane and dpds=4,4'-dipyridyldisulfide), were solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), fluorescent analysis and single-crystal X-ray diffraction. Complex 1 is of monoclinic system, space group P21/c with a=14.4370(17), b=8.4090(10), c=19.168(2)Å, β=104.5050(10)°, V=2252.8(5)Å3, Dc=1.639 g/cm3, Mr=555.81, Z=4, F(000)=1120, μ=1.022 mm-1, the final R=0.0269 and wR=0.0599 for 16656 observed reflections with I>2σ(I). 2 is isostructural to 1 with a=14.4175(11), b=8.4737(7), c=18.0120(14)Å, β=106.7220(10)°, V=2107.5(3)Å3, Dc=1.821 g/cm3, Mr=577.85, Z=4, F(000)=1152, μ=1.287 mm-1, the final R=0.0280 and wR=0.0705 for 15136 observed reflections with I>2σ(I). Both complexes present intimately related structures featuring infinite Cd-carboxylate helix of [CdⅡ (nbdc)(H2O)]n connected by bpp (or dpds) molecule to produce the 2D layer frameworks.
Two novel compounds, {[Cd(nbdc)(bpp)(H2O)]·H2O}n 1 and {[Cd(nbdc)(dpds)(H2O)]·H2O}n 2 (H2nbdc=4-nitro-1,2-benzenedicarboxylic acid, bpp=1,3-bis(4-pyridyl)propane and dpds=4,4'-dipyridyldisulfide), were solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), fluorescent analysis and single-crystal X-ray diffraction. Complex 1 is of monoclinic system, space group P21/c with a=14.4370(17), b=8.4090(10), c=19.168(2)Å, β=104.5050(10)°, V=2252.8(5)Å3, Dc=1.639 g/cm3, Mr=555.81, Z=4, F(000)=1120, μ=1.022 mm-1, the final R=0.0269 and wR=0.0599 for 16656 observed reflections with I>2σ(I). 2 is isostructural to 1 with a=14.4175(11), b=8.4737(7), c=18.0120(14)Å, β=106.7220(10)°, V=2107.5(3)Å3, Dc=1.821 g/cm3, Mr=577.85, Z=4, F(000)=1152, μ=1.287 mm-1, the final R=0.0280 and wR=0.0705 for 15136 observed reflections with I>2σ(I). Both complexes present intimately related structures featuring infinite Cd-carboxylate helix of [CdⅡ (nbdc)(H2O)]n connected by bpp (or dpds) molecule to produce the 2D layer frameworks.
2014, 33(5): 771-778
Abstract:
Pure and Mn-doped NaTaO3 nanoparticles were synthesized by a simple hydrothermal method. XRD and XPS results suggested that manganese ions were successfully doped into the NaTaO3 crystalline in Mn2+ state. UV-vis diffuse reflectance spectra revealed the obvious red-shift in the series of manganese doped NaTaO3 nanoparticles, resulting in a decrease in the band gap of NaTaO3 with the increase of Mn2+ doping concentration. The photo-degradation experiment indicated that manganese doped NaTaO3 showed good photocatalytic performance and methylene blue (MB) degradation is improved with lower doping concentration of manganese ions under visible light. The simulation of energy band structure by density functional theory unfolded that the substitution of Ta5+ ions by Mn2+ ions resulted in an intermediate band (IB) below the bottom of the conduction band (CB), which was mainly attributed to the state of Mn 3d.
Pure and Mn-doped NaTaO3 nanoparticles were synthesized by a simple hydrothermal method. XRD and XPS results suggested that manganese ions were successfully doped into the NaTaO3 crystalline in Mn2+ state. UV-vis diffuse reflectance spectra revealed the obvious red-shift in the series of manganese doped NaTaO3 nanoparticles, resulting in a decrease in the band gap of NaTaO3 with the increase of Mn2+ doping concentration. The photo-degradation experiment indicated that manganese doped NaTaO3 showed good photocatalytic performance and methylene blue (MB) degradation is improved with lower doping concentration of manganese ions under visible light. The simulation of energy band structure by density functional theory unfolded that the substitution of Ta5+ ions by Mn2+ ions resulted in an intermediate band (IB) below the bottom of the conduction band (CB), which was mainly attributed to the state of Mn 3d.
2014, 33(5): 779-784
Abstract:
The title compound 2-(5-(4-chlorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)-pyridine (C20H16ClN3, Mr=333.81) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a=10.9925(12), b=11.0378(12), c=14.2751(18)Å, β=98.074(11)°, V=1714.9(3)Å3, Z=4, Dc=1.293 g/cm3, μ(MoKα)=0.228 mm-1, F(000)=696, the final R=0.0521 and wR=0.1349 for 3495 observed reflections with I>2σ(I). Intermolecular C-H…π interactions and π-π stacking interactions stabilize the crystal structure. The binding study by fluorescence spectroscope titration showed that the title compound can selectively recognize Fe3+ in THF solution with fluorescence quenching.
The title compound 2-(5-(4-chlorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)-pyridine (C20H16ClN3, Mr=333.81) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a=10.9925(12), b=11.0378(12), c=14.2751(18)Å, β=98.074(11)°, V=1714.9(3)Å3, Z=4, Dc=1.293 g/cm3, μ(MoKα)=0.228 mm-1, F(000)=696, the final R=0.0521 and wR=0.1349 for 3495 observed reflections with I>2σ(I). Intermolecular C-H…π interactions and π-π stacking interactions stabilize the crystal structure. The binding study by fluorescence spectroscope titration showed that the title compound can selectively recognize Fe3+ in THF solution with fluorescence quenching.
2014, 33(5): 785-789
Abstract:
A novel [2+4+2]-macrocyclic compound 3 (C52H69N16O12, Mr=1109.53) containing bis(ethoxycarbonyl)glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=10.077(3), b=10.642(3), c=15.324(5)Å, α=96.704(5), β=102.304(5), γ=104.546(5)°, Z=2, V=1528.7(8)Å3, Dc=1.283 g/cm3, μ=0.097 mm-1, F(000)=628, R=0.0818 and wR (I>2σ(I))=0.2346 for 3034 observed reflections.
A novel [2+4+2]-macrocyclic compound 3 (C52H69N16O12, Mr=1109.53) containing bis(ethoxycarbonyl)glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=10.077(3), b=10.642(3), c=15.324(5)Å, α=96.704(5), β=102.304(5), γ=104.546(5)°, Z=2, V=1528.7(8)Å3, Dc=1.283 g/cm3, μ=0.097 mm-1, F(000)=628, R=0.0818 and wR (I>2σ(I))=0.2346 for 3034 observed reflections.
2014, 33(5): 790-794
Abstract:
The title compound cinobufagin 3-hemisuberate methyl ester (1) was isolated from the venom of Bufo bufo gargarizans CANTOR. The crystal structure of 1, C35H48O9, was determined by single-crystal X-ray diffraction analysis. It belongs to orthorhombic, space group P212121 with a=8.9338(3), b=16.2970(4), c=22.4019(6)Å, V=3261.59(16)Å3, Mr=612.73, Z=4, Dc=1.248 g/cm3, μ=0.725 mm-1, F(000)=1320, S=1.040, the final R=0.0374 and wR=0.0412 for 4458 unique reflections, of which 4088 were observed (I>2σ(I)). In the solid state, short intermolecular C-H…O interactions involving a methine and the ester carbonyl group in cinobufagin moiety and a methyl in the suberate moiety linked adjacent molecules into a three-dimensional network. Detailed analysis of the 1H-NMR data showed that X-ray structure of 1 would be expected to closely resemble the solution conformation in chloroform. Compound 1 was inactive for the inhibition of PC3 and HepG2 cancer cells, but the parent compound cinobufagin showed potent inhibition with IC50 values of 0.145 and 5.48 μM, respectively, indicating that esterification at C(3) decreased the cytotoxic effect of 1.
The title compound cinobufagin 3-hemisuberate methyl ester (1) was isolated from the venom of Bufo bufo gargarizans CANTOR. The crystal structure of 1, C35H48O9, was determined by single-crystal X-ray diffraction analysis. It belongs to orthorhombic, space group P212121 with a=8.9338(3), b=16.2970(4), c=22.4019(6)Å, V=3261.59(16)Å3, Mr=612.73, Z=4, Dc=1.248 g/cm3, μ=0.725 mm-1, F(000)=1320, S=1.040, the final R=0.0374 and wR=0.0412 for 4458 unique reflections, of which 4088 were observed (I>2σ(I)). In the solid state, short intermolecular C-H…O interactions involving a methine and the ester carbonyl group in cinobufagin moiety and a methyl in the suberate moiety linked adjacent molecules into a three-dimensional network. Detailed analysis of the 1H-NMR data showed that X-ray structure of 1 would be expected to closely resemble the solution conformation in chloroform. Compound 1 was inactive for the inhibition of PC3 and HepG2 cancer cells, but the parent compound cinobufagin showed potent inhibition with IC50 values of 0.145 and 5.48 μM, respectively, indicating that esterification at C(3) decreased the cytotoxic effect of 1.
2014, 33(5): 795-800
Abstract:
The title compound of physalin B (C28H32O9), a main active physalin of Physalis angulata L, was isolated from the whole plant of Physalis angulata L, and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21 with C28H32O9, a=12.4996(2), b=14.35620(10), c=14.75190(10)Å, V=2607.97(5)Å3, Z=4, Dc=1.382 mg/cm3, Mr=542.56, F(000)=1152, and μ=0.870 mm-1. The final R=0.0389 and wR=0.1037 for 47670 observed reflections (I>2σ(I)). The rigid molecule consists of eight fused rings involving two lactones. There are two C28H32O9 molecules in an symmetric unit, and the title compound is stacked into a 3D layer structure through hydrogen bonds. In the 5~20 μmol/L range, physalin B can significantly inhibit the secretion of inflammatory cytokines TNF-α and IL-6 on RAW264.7 cells. The results suggest that physalin B has anti-inflammatory activity in vitro.
The title compound of physalin B (C28H32O9), a main active physalin of Physalis angulata L, was isolated from the whole plant of Physalis angulata L, and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21 with C28H32O9, a=12.4996(2), b=14.35620(10), c=14.75190(10)Å, V=2607.97(5)Å3, Z=4, Dc=1.382 mg/cm3, Mr=542.56, F(000)=1152, and μ=0.870 mm-1. The final R=0.0389 and wR=0.1037 for 47670 observed reflections (I>2σ(I)). The rigid molecule consists of eight fused rings involving two lactones. There are two C28H32O9 molecules in an symmetric unit, and the title compound is stacked into a 3D layer structure through hydrogen bonds. In the 5~20 μmol/L range, physalin B can significantly inhibit the secretion of inflammatory cytokines TNF-α and IL-6 on RAW264.7 cells. The results suggest that physalin B has anti-inflammatory activity in vitro.
2014, 33(5): 801-806
Abstract:
The title compound β-sitosterol (C29H50O), an active phytosterol in many medicinal and edible plants, was characterized by X-ray diffraction analysis and extensive nuclear magnetic resonance (NMR) data. It crystallizes in monoclinic system, space group P21 with C29H50O·1/2H2O, a=9.4226(7), b=7.4824(9), c=36.889(3)Å, V=2597.0(4)Å3, Z=4, Dx=1.084 g/cm3, Mr=423.70, F(000)=948, and μ=0.064 mm-1. The final R=0.0886 and wR=0.2234 for 10157 observed reflections (I>2σ(I)). The molecular crystal structure of β-sitosterol shows relative stereochemistry of 24R-ethylcholest-5-en-3β-ol. The molecule is composed of one steroid nucleus (3 six-membered rings and 1 five-membered ring) and one sidechain of 10 carbons. There are two C29H50O molecules and one H2O molecule in a symmetrical unit, and the title compound is stacked into a special laminated structure through hydrogen bonds and van der Waal forces. The special laminated structure was first reported.
The title compound β-sitosterol (C29H50O), an active phytosterol in many medicinal and edible plants, was characterized by X-ray diffraction analysis and extensive nuclear magnetic resonance (NMR) data. It crystallizes in monoclinic system, space group P21 with C29H50O·1/2H2O, a=9.4226(7), b=7.4824(9), c=36.889(3)Å, V=2597.0(4)Å3, Z=4, Dx=1.084 g/cm3, Mr=423.70, F(000)=948, and μ=0.064 mm-1. The final R=0.0886 and wR=0.2234 for 10157 observed reflections (I>2σ(I)). The molecular crystal structure of β-sitosterol shows relative stereochemistry of 24R-ethylcholest-5-en-3β-ol. The molecule is composed of one steroid nucleus (3 six-membered rings and 1 five-membered ring) and one sidechain of 10 carbons. There are two C29H50O molecules and one H2O molecule in a symmetrical unit, and the title compound is stacked into a special laminated structure through hydrogen bonds and van der Waal forces. The special laminated structure was first reported.
