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2014 Volume 33 Issue 9
2014, 33(9): 1267-1274
Abstract:
The X2Ge=Si:(X=H, Me, F, Cl, Br, Ph, Ar…) is a new species. Its cycloaddition reaction is a new area for the study of silylene chemistry. The mechanism of cycloaddition reaction between singlet Cl2Ge=Si:and formaldehyde has been investigated with CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the[2+2] cycloaddition reaction. Owing to the 3p unoccupied orbital of Si:atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si:atom in intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring silylene makes it isomerize to a twisted four-membered ring product. The research result indicates the laws of cycloaddition reaction between X2Ge=Si:(X=H, Me, F, Cl, Br, Ph, Ar…) and the asymmetric π-bonded compounds, which are significant for the synthesis of small-ring and spiro-Si-heterocyclic ring compound involving Ge. The study extends the research area and enriches the research content of silylene chemistry.
The X2Ge=Si:(X=H, Me, F, Cl, Br, Ph, Ar…) is a new species. Its cycloaddition reaction is a new area for the study of silylene chemistry. The mechanism of cycloaddition reaction between singlet Cl2Ge=Si:and formaldehyde has been investigated with CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the[2+2] cycloaddition reaction. Owing to the 3p unoccupied orbital of Si:atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si:atom in intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring silylene makes it isomerize to a twisted four-membered ring product. The research result indicates the laws of cycloaddition reaction between X2Ge=Si:(X=H, Me, F, Cl, Br, Ph, Ar…) and the asymmetric π-bonded compounds, which are significant for the synthesis of small-ring and spiro-Si-heterocyclic ring compound involving Ge. The study extends the research area and enriches the research content of silylene chemistry.
2014, 33(9): 1275-1280
Abstract:
A new thiosemicarbazone compound derived from 1-phenyl-3-methyl-4-(2-thenoyl) pyrazolone-5 (HPMTP) and thiosemicarbazide has been synthesized and characterized by IR, HNMR, MS, elemental analysis, UV and single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, Cc space group with a=7.5925(8), b=20.263(2), c=11.4669(13) Å, β=107.825(8)°, V=1679.5(3) Å3, Z=4, R=0.0316 and wR=0.0687. The results of antibacterial activity test against Escherichia coli and Bacillus subtilis indicate that the compound possesses the same antibacterial activity as the contrast (Norfloxacin). Theoretical study of the forming mechanism to the title compound at the RHF/6-31G(d) level shows that there are two steps. The distal amino group of thiosemicarbazide is added to the 4-carbonyl group of HPMTP which forms TM. Then a dehydration reaction occurs in TM and generates a stable product PC.
A new thiosemicarbazone compound derived from 1-phenyl-3-methyl-4-(2-thenoyl) pyrazolone-5 (HPMTP) and thiosemicarbazide has been synthesized and characterized by IR, HNMR, MS, elemental analysis, UV and single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, Cc space group with a=7.5925(8), b=20.263(2), c=11.4669(13) Å, β=107.825(8)°, V=1679.5(3) Å3, Z=4, R=0.0316 and wR=0.0687. The results of antibacterial activity test against Escherichia coli and Bacillus subtilis indicate that the compound possesses the same antibacterial activity as the contrast (Norfloxacin). Theoretical study of the forming mechanism to the title compound at the RHF/6-31G(d) level shows that there are two steps. The distal amino group of thiosemicarbazide is added to the 4-carbonyl group of HPMTP which forms TM. Then a dehydration reaction occurs in TM and generates a stable product PC.
2014, 33(9): 1281-1286
Abstract:
A new binuclear copper complex,[Cu2L2(pht)2]2·H2O (Hpht=5,5-diphenylhydantoin, i.e. phenytoin; L=2-diethylaminoethanol), has been synthesized by the solvothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a=31.918(3), b=12.9222(15), c=19.868(2) Å, β=98.762(2)°, V=8098.8(16) Å3, Dc=1.429 Mg/m3, Z=4, F(000)=3640, μ=1.107 mm-1, R=0.0560 and wR=0.1276 (I > 2σ(I)). Each copper(Ⅱ) in a molecule is coordinated with N and O atoms from ligand L and N atom from ligand Hpht in a tetradentate manner. Moreover, two copper(Ⅱ) centers are bridged by two O atoms of hydroxyl groups from two L ligands to form a slightly distorted binuclear {Cu2O2} diamond configuration. In addition, the interaction of this complex with calf thymus DNA (CT-DNA) was investigated by UV-vis spectrum and viscometry, and the complex may bind to DNA through intercalation.
A new binuclear copper complex,[Cu2L2(pht)2]2·H2O (Hpht=5,5-diphenylhydantoin, i.e. phenytoin; L=2-diethylaminoethanol), has been synthesized by the solvothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a=31.918(3), b=12.9222(15), c=19.868(2) Å, β=98.762(2)°, V=8098.8(16) Å3, Dc=1.429 Mg/m3, Z=4, F(000)=3640, μ=1.107 mm-1, R=0.0560 and wR=0.1276 (I > 2σ(I)). Each copper(Ⅱ) in a molecule is coordinated with N and O atoms from ligand L and N atom from ligand Hpht in a tetradentate manner. Moreover, two copper(Ⅱ) centers are bridged by two O atoms of hydroxyl groups from two L ligands to form a slightly distorted binuclear {Cu2O2} diamond configuration. In addition, the interaction of this complex with calf thymus DNA (CT-DNA) was investigated by UV-vis spectrum and viscometry, and the complex may bind to DNA through intercalation.
2014, 33(9): 1287-1292
Abstract:
Tricyclohexyltin 4-amino-3-methyl-benzoate (1) and tricyclohexyltin 3,4-dimethoxybenzoate (2) were synthesized and their crystal structures were determined by X-ray diffraction. Compound 1 belongs to the monoclinic system, space group P21/c with a=14.0554(15), b=11.6947(13), c=16.2720(17) Å, Z=4, V=2565.7(5) Å3, Dc=1.341 g·cm-3, μ(MoKα)=1.016 mm-1, F(000)=1080, R=0.0833 and wR=0.2964. Compound 2 is of monoclinic system, space group C2/c with a=17.8712(6), b=8.4433(3), c=35.5783(13) Å, Z=8, V=5366.8(3) Å3, Dc=1.360 g·cm-3, μ(MoKα)=0.980 mm-1, F(000)=2288, R=0.0549, wR=0.1279. In compounds 1 and 2, the central Sn atom is coordinated in a tetradentate manner to assume a distorted tetrahedral configuration. Preliminary biological tests showed that these two compounds have strong acaricidal activity.
Tricyclohexyltin 4-amino-3-methyl-benzoate (1) and tricyclohexyltin 3,4-dimethoxybenzoate (2) were synthesized and their crystal structures were determined by X-ray diffraction. Compound 1 belongs to the monoclinic system, space group P21/c with a=14.0554(15), b=11.6947(13), c=16.2720(17) Å, Z=4, V=2565.7(5) Å3, Dc=1.341 g·cm-3, μ(MoKα)=1.016 mm-1, F(000)=1080, R=0.0833 and wR=0.2964. Compound 2 is of monoclinic system, space group C2/c with a=17.8712(6), b=8.4433(3), c=35.5783(13) Å, Z=8, V=5366.8(3) Å3, Dc=1.360 g·cm-3, μ(MoKα)=0.980 mm-1, F(000)=2288, R=0.0549, wR=0.1279. In compounds 1 and 2, the central Sn atom is coordinated in a tetradentate manner to assume a distorted tetrahedral configuration. Preliminary biological tests showed that these two compounds have strong acaricidal activity.
2014, 33(9): 1293-1299
Abstract:
A Zn(Ⅱ) coordination polymer[Zn(NIP)(3,3'-bpt)]·H2O (1, NIP=5-nitroisophthalate, 3,3'-bpt=1H-3,5-bis(3-pyridyl)-1,2,4-triazolate) has been synthesized by the hydrothermal reaction at 140℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2NIP and two nitrogen atoms from two 3,3'-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.
A Zn(Ⅱ) coordination polymer[Zn(NIP)(3,3'-bpt)]·H2O (1, NIP=5-nitroisophthalate, 3,3'-bpt=1H-3,5-bis(3-pyridyl)-1,2,4-triazolate) has been synthesized by the hydrothermal reaction at 140℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2NIP and two nitrogen atoms from two 3,3'-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.
2014, 33(9): 1300-1304
Abstract:
A new complex[Cu(L)(1,10-phen)]n (1, L=N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P21/c with a=11.481(2), b=18.094(4), c=8.5198(17) Å, β=102.26(3)°,V=1729.5(6) Å3, Z=4, Dc=1.759 g/cm3, F(000)=932, μ=1.422 mm-1, R=0.0368 and wR=0.0893. In 1, the Cu(Ⅱ) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ) units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.
A new complex[Cu(L)(1,10-phen)]n (1, L=N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P21/c with a=11.481(2), b=18.094(4), c=8.5198(17) Å, β=102.26(3)°,V=1729.5(6) Å3, Z=4, Dc=1.759 g/cm3, F(000)=932, μ=1.422 mm-1, R=0.0368 and wR=0.0893. In 1, the Cu(Ⅱ) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ) units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.
2014, 33(9): 1305-1310
Abstract:
A new mixed-valence cyanide-bridged complex, Br3Fe(μ-NC)RuBr(dppm)2 (dppm=bis(diphenylphosphino)methane), was obtained through the reaction between trans-(dppm)2ClRuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer (MMCT) and this complex is Class Ⅱ mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.
A new mixed-valence cyanide-bridged complex, Br3Fe(μ-NC)RuBr(dppm)2 (dppm=bis(diphenylphosphino)methane), was obtained through the reaction between trans-(dppm)2ClRuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer (MMCT) and this complex is Class Ⅱ mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.
2014, 33(9): 1311-1318
Abstract:
Hydrothermal reactions of two imidazole derivatives (1,3,5-tib=1,3,5-tris(1H-imidazol-1-yl)benzene, 1,4-bimb=1,4-bis(1H-imidazol-1-ylmethyl)benzene) and the ZnⅡ cations in the presence of oxalic acid (H2ox) afford two coordination polymers, namely, {[Zn(ox)(1,3,5 tib)]·2(H2O)}n (1) and[Zn1.5(ox)1.5(1,4-bimb)1.5]n (2). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction (PXRD) analyses. Both complexes 1 and 2 are based on the 1D zigzag[Zn(ox)]n chains, and their final structures are controlled by the two different imidazole linkers, which expanded the structure along different directions, finally giving a 3D dia net for 1 and a 2D sql layer for 2. Moreover, the luminescent properties of 1 and 2 have been investigated.
Hydrothermal reactions of two imidazole derivatives (1,3,5-tib=1,3,5-tris(1H-imidazol-1-yl)benzene, 1,4-bimb=1,4-bis(1H-imidazol-1-ylmethyl)benzene) and the ZnⅡ cations in the presence of oxalic acid (H2ox) afford two coordination polymers, namely, {[Zn(ox)(1,3,5 tib)]·2(H2O)}n (1) and[Zn1.5(ox)1.5(1,4-bimb)1.5]n (2). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction (PXRD) analyses. Both complexes 1 and 2 are based on the 1D zigzag[Zn(ox)]n chains, and their final structures are controlled by the two different imidazole linkers, which expanded the structure along different directions, finally giving a 3D dia net for 1 and a 2D sql layer for 2. Moreover, the luminescent properties of 1 and 2 have been investigated.
2014, 33(9): 1319-1325
Abstract:
The Schiff base organotin(IV) complex {[4-Et2NC6H3(O)C=NC6H3(O)-5-NO2](n-Bu2Sn)}2 has been synthesized via the reaction between 4-(diethylamino) salicylaldehyde-2-amino-4-nitrophenol Schiff base (H2L) and dibutyltin oxide. Complex C1 has been characterized by IR, 1H NMR, 13C NMR spectra, and elemental analysis, and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a=15.6559(8), b=9.1657(5), c=18.8351(10) Å, β=107.3440(10)°, Z=4, V=2579.9(2) Å3, Dc=1.442 Mg·m-3, μ(MoKα)=1.025 mm-1, F(000)=1152, R=0.0250 and wR=0.0633. The central Sn atom is coordinated in a hexadentate manner to assume a distorted octahedral configuration. Complex C1 was studied by TGA analysis in air atmosphere. The interaction between complex C1 and the herring sperm DNA was realized through the intercalation of the complex based on the studies by EB fluorescent probe.
The Schiff base organotin(IV) complex {[4-Et2NC6H3(O)C=NC6H3(O)-5-NO2](n-Bu2Sn)}2 has been synthesized via the reaction between 4-(diethylamino) salicylaldehyde-2-amino-4-nitrophenol Schiff base (H2L) and dibutyltin oxide. Complex C1 has been characterized by IR, 1H NMR, 13C NMR spectra, and elemental analysis, and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a=15.6559(8), b=9.1657(5), c=18.8351(10) Å, β=107.3440(10)°, Z=4, V=2579.9(2) Å3, Dc=1.442 Mg·m-3, μ(MoKα)=1.025 mm-1, F(000)=1152, R=0.0250 and wR=0.0633. The central Sn atom is coordinated in a hexadentate manner to assume a distorted octahedral configuration. Complex C1 was studied by TGA analysis in air atmosphere. The interaction between complex C1 and the herring sperm DNA was realized through the intercalation of the complex based on the studies by EB fluorescent probe.
2014, 33(9): 1326-1332
Abstract:
Two new Zn(Ⅱ)-MOFs were synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by the condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecarboxylic acid hydrazide. In different mixed solvents, we get two new isomorphism compounds,[Zn(L)2]·C4H8O2·2MeOH (1) and[Zn(L)2]·CH2Cl2·2MeOH (2). Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a=13.856(4), b=14.156(4), c=9.620(3) Å, β=110.167(5>)°, V=1771.3(9) Å3, Dc=1.500 g/cm3, C38H38N8O8Zn, Mr=800.13, F(000)=832, μ(MoKα)=0.761 mm-1, Z=2, the final R=0.0596 and wR=0.1221 for 2112 observed reflections (I > 2σ(I)). Compound 2 belongs to monoclinic, space group P21/c, with a=13.575(3), b=14.130(3), c=9.485(2) Å, β=107.908(3)°, V=1731.2(6) Å3, Dc=1.529 g/cm3, C35H32C12N8O6Zn, Mr=796.96, F(000)=820, μ(MoKα)=0.926 mm-1, Z=2, the final R=0.0527 and wR=0.1395 for 2501 observed reflections (I > 2σ(I)). The Zn(Ⅱ) centers in both 1 and 2 display a distorted octahedral coordination geometry. The octahedral Zn(Ⅱ) nodes and L linkages build up 2-D nets consisting of parallelogram-like grids in the ab plane. The neighboring nets stack through hydrogen bonds to generate 3-D rhombic channels. In 1, the 1,4-dioxane and MeOH guests alternatively arrange in the channels and effectively take up the free space; while in 2, the CH2Cl2 guests are arranged in the channels. In addition, the encapsulated MeOH molecules are bonded to the framework by hydrogen bonds.
Two new Zn(Ⅱ)-MOFs were synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by the condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecarboxylic acid hydrazide. In different mixed solvents, we get two new isomorphism compounds,[Zn(L)2]·C4H8O2·2MeOH (1) and[Zn(L)2]·CH2Cl2·2MeOH (2). Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a=13.856(4), b=14.156(4), c=9.620(3) Å, β=110.167(5>)°, V=1771.3(9) Å3, Dc=1.500 g/cm3, C38H38N8O8Zn, Mr=800.13, F(000)=832, μ(MoKα)=0.761 mm-1, Z=2, the final R=0.0596 and wR=0.1221 for 2112 observed reflections (I > 2σ(I)). Compound 2 belongs to monoclinic, space group P21/c, with a=13.575(3), b=14.130(3), c=9.485(2) Å, β=107.908(3)°, V=1731.2(6) Å3, Dc=1.529 g/cm3, C35H32C12N8O6Zn, Mr=796.96, F(000)=820, μ(MoKα)=0.926 mm-1, Z=2, the final R=0.0527 and wR=0.1395 for 2501 observed reflections (I > 2σ(I)). The Zn(Ⅱ) centers in both 1 and 2 display a distorted octahedral coordination geometry. The octahedral Zn(Ⅱ) nodes and L linkages build up 2-D nets consisting of parallelogram-like grids in the ab plane. The neighboring nets stack through hydrogen bonds to generate 3-D rhombic channels. In 1, the 1,4-dioxane and MeOH guests alternatively arrange in the channels and effectively take up the free space; while in 2, the CH2Cl2 guests are arranged in the channels. In addition, the encapsulated MeOH molecules are bonded to the framework by hydrogen bonds.
2014, 33(9): 1333-1338
Abstract:
One novel cobalt coordination polymer, {[Co(HTCB)(4,4'-btb)]·H2O}n (1, H3TCB=1,3,5-tris(4-carboxyphenyl)benzene, 4,4'-btb=4,4'-bis(1,2,4-triazol-3-yl)biphenyl), has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql[Co(HTCB)(4,4'-btb)] sheet based on the 1D[Co(HTCB)]n chains and 1D[Co(4,4'-btb)]n chains. The crystal of 1 crystallizes in triclinic, space group P1 with a=9.529(12), b=13.914(16), c=14.906(17) Å, V=1903(4) Å3, Z=2, C45H34N6CoO7, Mr=829.71, Dc=1.448 g/cm3, F(000)=858 and μ(MoKα)=0.514 mm-1. The final R=0.0655 and wR=0.1136 for 6603 observed reflections with I > 2σ(I) and R=0.1136 and wR=0.1747 for all data.
One novel cobalt coordination polymer, {[Co(HTCB)(4,4'-btb)]·H2O}n (1, H3TCB=1,3,5-tris(4-carboxyphenyl)benzene, 4,4'-btb=4,4'-bis(1,2,4-triazol-3-yl)biphenyl), has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql[Co(HTCB)(4,4'-btb)] sheet based on the 1D[Co(HTCB)]n chains and 1D[Co(4,4'-btb)]n chains. The crystal of 1 crystallizes in triclinic, space group P1 with a=9.529(12), b=13.914(16), c=14.906(17) Å, V=1903(4) Å3, Z=2, C45H34N6CoO7, Mr=829.71, Dc=1.448 g/cm3, F(000)=858 and μ(MoKα)=0.514 mm-1. The final R=0.0655 and wR=0.1136 for 6603 observed reflections with I > 2σ(I) and R=0.1136 and wR=0.1747 for all data.
2014, 33(9): 1339-1345
Abstract:
A new Cu(Ⅱ) coordination polymer,[Cu2(mip)2(bmix)]n (bmix=1,4-bis(2-methylimidazole-1-ylmethyl)benzene, H2mip=5-methylisophthalic acid), has been hydrothermally synthesized and characterized by elemental analyses, IR, TGA and single-crystal X-ray diffraction. The title compound belongs to the triclinic system, space group P1 with a=9.435(5), b=12.241(6), c=13.666(6) Å, β=94.396(8)°, V=1565.5(13) Å3, Z=2, C34H30Cu2N4O8, Mr=749.70, Dc=1.590 g/cm3, μ=1.419 mm-1 and F(000)=768. The title metal-organic coordination polymer exhibits the first two-fold interpenetrated pcu topological structure assembled by two types of dinuclear copper(Ⅱ) clusters and a flexible bis(imidazole)-based ligand. In addition, the fluorescence and catalytic performances of the complex for the degradation of Congo red azo dye in Fenton-like process were presented.
A new Cu(Ⅱ) coordination polymer,[Cu2(mip)2(bmix)]n (bmix=1,4-bis(2-methylimidazole-1-ylmethyl)benzene, H2mip=5-methylisophthalic acid), has been hydrothermally synthesized and characterized by elemental analyses, IR, TGA and single-crystal X-ray diffraction. The title compound belongs to the triclinic system, space group P1 with a=9.435(5), b=12.241(6), c=13.666(6) Å, β=94.396(8)°, V=1565.5(13) Å3, Z=2, C34H30Cu2N4O8, Mr=749.70, Dc=1.590 g/cm3, μ=1.419 mm-1 and F(000)=768. The title metal-organic coordination polymer exhibits the first two-fold interpenetrated pcu topological structure assembled by two types of dinuclear copper(Ⅱ) clusters and a flexible bis(imidazole)-based ligand. In addition, the fluorescence and catalytic performances of the complex for the degradation of Congo red azo dye in Fenton-like process were presented.
2014, 33(9): 1346-1352
Abstract:
An organic-inorganic hybrid based on α-Keggin-typed[BW12O40]5- anionic cluster,[Co(BIIM)3]2H[BW12O40]·7H2O (BIIM=2,2'-biimidazole), was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a=12.3490(10), b=33.270(3), c=18.9660(16) Å, β=105.9950(10)°, V=7490.5(11) Å3, C36H50BCo2N24O47W12, Mr=3905.80, Dc=3.451g/cm3, μ(MoKα)=18.886 mm-1, F(000)=6972, Z=4, S=1.004, the final R=0.0404 and wR=0.0914 for 14683 observed reflections (I > 2σ(I)). The compound consists of two isolated[Co(BIIM)3]2+ cations and one[BW12O40]5- anion, in which each Co2+ ion is coordinated by six N atoms from three BIIM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N-H…O(polyoxometalate and water) hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W-Oterminal…πimidazole ring interactions which cooperate with the classical N-H…O hydrogen bonds to stabilize the structural packing.
An organic-inorganic hybrid based on α-Keggin-typed[BW12O40]5- anionic cluster,[Co(BIIM)3]2H[BW12O40]·7H2O (BIIM=2,2'-biimidazole), was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a=12.3490(10), b=33.270(3), c=18.9660(16) Å, β=105.9950(10)°, V=7490.5(11) Å3, C36H50BCo2N24O47W12, Mr=3905.80, Dc=3.451g/cm3, μ(MoKα)=18.886 mm-1, F(000)=6972, Z=4, S=1.004, the final R=0.0404 and wR=0.0914 for 14683 observed reflections (I > 2σ(I)). The compound consists of two isolated[Co(BIIM)3]2+ cations and one[BW12O40]5- anion, in which each Co2+ ion is coordinated by six N atoms from three BIIM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N-H…O(polyoxometalate and water) hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W-Oterminal…πimidazole ring interactions which cooperate with the classical N-H…O hydrogen bonds to stabilize the structural packing.
2014, 33(9): 1353-1359
Abstract:
A new energetic organic potassium salt bis(dinitromethyl)difurazanyl ether potassium salt[K2(BDFE)] was synthesized, and structurally characterized by elemental analysis, IR spectra, 13C NMR and single-crystal X-ray diffraction. K2(BDFE) crystallizes in monoclinic system, space group C2/c with a=17.342(3), b=12.6943(17), c=8.0972(11) Å, β=110.630(2)°, V=1668.3(4) Å3, Z=4, Dc=2.000 g/cm3, F(000)=1000, μ=0.675 mm-1, S=1.058, the final R=0.0499 and wR=0.1452. The K ion is eight-coordinated with eight O atoms from one water molecule and four bis(dinitromethyl)difurazanyl ethers (BDFE), forming a distorted dodecahedral structure. Thermal decomposition of the title complex was studied by using DSC and TG-DTG. There are primarily two exothermic decomposition processes between 200 and 370℃.
A new energetic organic potassium salt bis(dinitromethyl)difurazanyl ether potassium salt[K2(BDFE)] was synthesized, and structurally characterized by elemental analysis, IR spectra, 13C NMR and single-crystal X-ray diffraction. K2(BDFE) crystallizes in monoclinic system, space group C2/c with a=17.342(3), b=12.6943(17), c=8.0972(11) Å, β=110.630(2)°, V=1668.3(4) Å3, Z=4, Dc=2.000 g/cm3, F(000)=1000, μ=0.675 mm-1, S=1.058, the final R=0.0499 and wR=0.1452. The K ion is eight-coordinated with eight O atoms from one water molecule and four bis(dinitromethyl)difurazanyl ethers (BDFE), forming a distorted dodecahedral structure. Thermal decomposition of the title complex was studied by using DSC and TG-DTG. There are primarily two exothermic decomposition processes between 200 and 370℃.
2014, 33(9): 1360-1366
Abstract:
Solvothermal reactions of Zn(NO3)2·6H2O with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional (3D) hetero-metallic inorganic-organic hybrid framework[ZnK2(m-BDC)2(H2O)2]n (1, m-H2BDC=benzene-1,3-dicarboxylic acid). The crystal was characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction analysis. Complex 1 is of orthogonal crystal system, acentric space group Cmc21 with a=19.764(6), b=19.948(6), c=12.039(4) Å, V=4746(3) Å3, Z=4, C32H20O19K4Zn2, Mr=995.66, Dc=1.393 g/cm3, F(000)=2000 and μ=1.426 mm-1. The final R=0.0761 and wR=0.1841. The crystal exhibits remarkable blue luminescence emissions with high quantum yield of 56.02% and displays modest powder SHG efficiency of about 0.7 times that produced by a potassium dihydrogen phosphate (KDP) powder. In addition, it also exhibits potential ferroelectric property.
Solvothermal reactions of Zn(NO3)2·6H2O with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional (3D) hetero-metallic inorganic-organic hybrid framework[ZnK2(m-BDC)2(H2O)2]n (1, m-H2BDC=benzene-1,3-dicarboxylic acid). The crystal was characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction analysis. Complex 1 is of orthogonal crystal system, acentric space group Cmc21 with a=19.764(6), b=19.948(6), c=12.039(4) Å, V=4746(3) Å3, Z=4, C32H20O19K4Zn2, Mr=995.66, Dc=1.393 g/cm3, F(000)=2000 and μ=1.426 mm-1. The final R=0.0761 and wR=0.1841. The crystal exhibits remarkable blue luminescence emissions with high quantum yield of 56.02% and displays modest powder SHG efficiency of about 0.7 times that produced by a potassium dihydrogen phosphate (KDP) powder. In addition, it also exhibits potential ferroelectric property.
2014, 33(9): 1367-1374
Abstract:
A complex[NiL2] was synthesized, in which L, or to be exact, a Schiff base ligand (HL), was derived from the condensation of 1-phenyl-3-methyl-4-phenylacetyl-5-pyrazolone (PMPAP) with L-phenylalanine methyl ester. They were characterized by IR and single-crystal X-ray diffraction. Green block crystals of both ligand and its complex were grown at room temperature. The ligand, which consists of two individual fragments, crystalizes in the P1 space group (a=5.6268(5), b=10.6892(11) and c=19.4869(18) Å). The complex crystalizes in the P21 space group (a=21.4076(18), b=9.4792(8) and c=25.287(2) Å), which consists of a nickel six-coordinated compound. Every fragment is a distorted octahedron with four oxygen and two nitrogen atoms. The Schiff base ligand (HL) and its complex have been tested in vitro to evaluate their antibacterial activity against bacteria Escherichia Coli and Bacillus subtilis. It is found that the complex has higher activity than the corresponding free Schiff base ligand (HL) against the same bacterial.
A complex[NiL2] was synthesized, in which L, or to be exact, a Schiff base ligand (HL), was derived from the condensation of 1-phenyl-3-methyl-4-phenylacetyl-5-pyrazolone (PMPAP) with L-phenylalanine methyl ester. They were characterized by IR and single-crystal X-ray diffraction. Green block crystals of both ligand and its complex were grown at room temperature. The ligand, which consists of two individual fragments, crystalizes in the P1 space group (a=5.6268(5), b=10.6892(11) and c=19.4869(18) Å). The complex crystalizes in the P21 space group (a=21.4076(18), b=9.4792(8) and c=25.287(2) Å), which consists of a nickel six-coordinated compound. Every fragment is a distorted octahedron with four oxygen and two nitrogen atoms. The Schiff base ligand (HL) and its complex have been tested in vitro to evaluate their antibacterial activity against bacteria Escherichia Coli and Bacillus subtilis. It is found that the complex has higher activity than the corresponding free Schiff base ligand (HL) against the same bacterial.
2014, 33(9): 1375-1382
Abstract:
A novel benzisothiazolin-3-one derivative, 2-(benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) acetamide (8), was synthesized from the initial compound benzo[d]isothiazol-3(2H)-one (BIT) 1 and 4-fluoroaniline 3. The structure of the target compound 8 was determined by elemental analyses, IR and 1H NMR. The single crystals of intermediate compound 6 and the target compound 8 were obtained and determined by X-ray diffraction analysis. The preliminary biological activity was also evaluated and the results showed the target compound exhibited a good anti-microbial activity.
A novel benzisothiazolin-3-one derivative, 2-(benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) acetamide (8), was synthesized from the initial compound benzo[d]isothiazol-3(2H)-one (BIT) 1 and 4-fluoroaniline 3. The structure of the target compound 8 was determined by elemental analyses, IR and 1H NMR. The single crystals of intermediate compound 6 and the target compound 8 were obtained and determined by X-ray diffraction analysis. The preliminary biological activity was also evaluated and the results showed the target compound exhibited a good anti-microbial activity.
2014, 33(9): 1383-1387
Abstract:
A new 4,5-diaryl-1H-imidazole was synthesized and characterized by 1H NMR, ESI-MS, elemental analysis and FT-IR. The crystal structure of the title compound (C19H16C12N2O2, Mr=375.24) has been determined by single-crystal X-ray diffraction. Crystal parameters:monoclinic system, space group P21/n, a=14.349(3), b=8.7918(18), c=15.352(3) Å, β=108.56(3)°, V=1836.1(6) Å3, Z=4, F(000)=776, Dc=1.357 g/cm3, μ=0.368 mm-1, the final R=0.0502 and wR=0.1066 for 2324 observed reflections with I > 2σ(I). A total of 16117 reflections were collected, of which 3615 were independent (Rint=0.0595). The preliminary bioassay suggested that the title compound exhibits distinct effective inhibition on the proliferation of cancer cell lines.
A new 4,5-diaryl-1H-imidazole was synthesized and characterized by 1H NMR, ESI-MS, elemental analysis and FT-IR. The crystal structure of the title compound (C19H16C12N2O2, Mr=375.24) has been determined by single-crystal X-ray diffraction. Crystal parameters:monoclinic system, space group P21/n, a=14.349(3), b=8.7918(18), c=15.352(3) Å, β=108.56(3)°, V=1836.1(6) Å3, Z=4, F(000)=776, Dc=1.357 g/cm3, μ=0.368 mm-1, the final R=0.0502 and wR=0.1066 for 2324 observed reflections with I > 2σ(I). A total of 16117 reflections were collected, of which 3615 were independent (Rint=0.0595). The preliminary bioassay suggested that the title compound exhibits distinct effective inhibition on the proliferation of cancer cell lines.
2014, 33(9): 1388-1394
Abstract:
The new title compound 4-chloro-N-(2-(2-nitrophenyl)acetoxy)-N-(m-tolyl)benzamide (C22H17ClN2O5, Mr=424.82) has been synthesized via the reaction of 4-chloro-N-hydroxy-N-(m-tolyl)benzamide with 2-(2-nitrophenyl)acetyl chloride. The structure of the product was confirmed by 1H NMR, 13C NMR, IR, HRMS (ESI) and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=13.0269(10), b=6.7251(6), c=23.9313(16) Å, β=99.931(6)°, V=2065.1(3) Å3, Z=4, Dc=1.366 g/cm3, F(000)=880, μ=0.221 mm-1, the final R=0.0600 and wR=0.1754 for 1981 observed reflections (I > 2σ(I)). X-ray analysis indicates that the chloro-phenyl ring (C(10)~C(15)) and the methyl-substituted benzene ring (C(16)~C(21)) are not coplanar with the nitro-substituted benzene ring (C(1)~C(6)), with the dihedral angle to be 70.78° and 63.72°, respectively. Hydrogen bonds C(2)-H(2)…O(2) and C(7)-H(7B)…O(5) are observed.
The new title compound 4-chloro-N-(2-(2-nitrophenyl)acetoxy)-N-(m-tolyl)benzamide (C22H17ClN2O5, Mr=424.82) has been synthesized via the reaction of 4-chloro-N-hydroxy-N-(m-tolyl)benzamide with 2-(2-nitrophenyl)acetyl chloride. The structure of the product was confirmed by 1H NMR, 13C NMR, IR, HRMS (ESI) and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=13.0269(10), b=6.7251(6), c=23.9313(16) Å, β=99.931(6)°, V=2065.1(3) Å3, Z=4, Dc=1.366 g/cm3, F(000)=880, μ=0.221 mm-1, the final R=0.0600 and wR=0.1754 for 1981 observed reflections (I > 2σ(I)). X-ray analysis indicates that the chloro-phenyl ring (C(10)~C(15)) and the methyl-substituted benzene ring (C(16)~C(21)) are not coplanar with the nitro-substituted benzene ring (C(1)~C(6)), with the dihedral angle to be 70.78° and 63.72°, respectively. Hydrogen bonds C(2)-H(2)…O(2) and C(7)-H(7B)…O(5) are observed.
2014, 33(9): 1395-1400
Abstract:
Twelve Mannich base derivatives of 1,2-benzisothiazolin-3-one were synthesized by the reaction of 1,2-benzisothiazol-3(2H)-one (BIT) with different amines and formaldehyde. All the compounds were characterized by elemental analysis, IR spectroscopy, MS and 1H NMR. The crystal structure for 2,2'-methylenebis(benzo[d]isothiazol-3(2H)-one) (3) has been determined by X-ray single-crystal structure analysis. Compound 3 (C15H10N2O2S2) crystallizes in the monoclinic system, space group C2/c with a=25.052(8), b=4.510(1), c=11.948(4) Å, β=100.992(4)°, V=1325.2(7) Å3, Mr=314.37, Dc=1.576 Mg·m-3, μ=0.25 mm-1, F(000)=648, Z=4, R=0.034 and wR=0.087. The preliminary biological test indicated that the compounds (2b, 2c) showed growth inhibitory activity against the gram-positive and gram-negative bacteria.
Twelve Mannich base derivatives of 1,2-benzisothiazolin-3-one were synthesized by the reaction of 1,2-benzisothiazol-3(2H)-one (BIT) with different amines and formaldehyde. All the compounds were characterized by elemental analysis, IR spectroscopy, MS and 1H NMR. The crystal structure for 2,2'-methylenebis(benzo[d]isothiazol-3(2H)-one) (3) has been determined by X-ray single-crystal structure analysis. Compound 3 (C15H10N2O2S2) crystallizes in the monoclinic system, space group C2/c with a=25.052(8), b=4.510(1), c=11.948(4) Å, β=100.992(4)°, V=1325.2(7) Å3, Mr=314.37, Dc=1.576 Mg·m-3, μ=0.25 mm-1, F(000)=648, Z=4, R=0.034 and wR=0.087. The preliminary biological test indicated that the compounds (2b, 2c) showed growth inhibitory activity against the gram-positive and gram-negative bacteria.
2014, 33(9): 1401-1408
Abstract:
A novel spherical cellulose adsorbent has been prepared by homogeneous graft polymerization of N,N'-methylenebisacrylamide (MBA) onto cellulose in an ionic liquid, 1-N-butyl-3-methylimidazolium chloride (BMIMCl), which was then partially amine methylated through Mannich reaction to get bifunctionalized materials containing both amide and sulphinate moities. Factors affecting the attachment of functional groups were investigated. The adsorbent was characterized by Elemental Analysis (EA), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM). Cellulose adsorbent was then tested for its potential applications in the reduction adsorption of trichloroacetic acid (TCAA) from aqueous solutions.
A novel spherical cellulose adsorbent has been prepared by homogeneous graft polymerization of N,N'-methylenebisacrylamide (MBA) onto cellulose in an ionic liquid, 1-N-butyl-3-methylimidazolium chloride (BMIMCl), which was then partially amine methylated through Mannich reaction to get bifunctionalized materials containing both amide and sulphinate moities. Factors affecting the attachment of functional groups were investigated. The adsorbent was characterized by Elemental Analysis (EA), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM). Cellulose adsorbent was then tested for its potential applications in the reduction adsorption of trichloroacetic acid (TCAA) from aqueous solutions.
2014, 33(9): 1409-1414
Abstract:
A new one-dimensional molecule based on the linkage of[Mo7O24] clusters and[BiL] (L=pyridine-2,6-dicarboxylic acid) assembles under ambient conditions. The title compound was characterized by X-ray powder diffraction, IR and UV spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. Crystal data:C7H38BiMo7N5O37, Mr=1664.95, monoclinic, space group C2/c, a=24.312(2), b=21.4869(18), c=18.5423(16) Å, β=111.6490(10)°, V=9002.9(13) Å3, Z=8, μ=5.883 mm-1, F(000)=6304, GOF=1.045, R=0.0365 and wR=0.1062.
A new one-dimensional molecule based on the linkage of[Mo7O24] clusters and[BiL] (L=pyridine-2,6-dicarboxylic acid) assembles under ambient conditions. The title compound was characterized by X-ray powder diffraction, IR and UV spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. Crystal data:C7H38BiMo7N5O37, Mr=1664.95, monoclinic, space group C2/c, a=24.312(2), b=21.4869(18), c=18.5423(16) Å, β=111.6490(10)°, V=9002.9(13) Å3, Z=8, μ=5.883 mm-1, F(000)=6304, GOF=1.045, R=0.0365 and wR=0.1062.
