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2014 Volume 33 Issue 11
2014, 33(11): 1573-1579
doi: 10.14102/j.cnki.0254-5861.2011-0331
Abstract:
A novel pyrazole derivative ligand, BTA (BTA=bis-(4-ethoxy-phenyl)-[4-(tripyrazol-1-yl-methyl)-phenyl]-amine), was synthesized and fully characterized by 1H-NMR, MALDI-TOF-MS spectra and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1, with a=11.827(1), b=16.000(2), c=16.527(2)Å, α=108.510(1), β=91.116(5), γ=101.734(1)°, V=2894.5(6)Å3, Z=1, Dc=1.262 g/m3, F(000)=1162, Mr=545.63, μ=0.083 mm-1 , the final R=0.0728 and wR=0.2213 for 7541 observed reflections with I>2σ(I). The structural analysis revealed that three pyrazole units are attached to the same carbon atom connected with bis-(4-ethoxy-phenyl)-phenyl-amine group. UV-vis spectral features of the ligand in various solutions were explained by time dependent density functional theory (TD-DFT). It was also found that the ligand (BTA) exhibits an exclusively selective and sensitive response toward Fe3+ using UV-vis spectroscopic method.
A novel pyrazole derivative ligand, BTA (BTA=bis-(4-ethoxy-phenyl)-[4-(tripyrazol-1-yl-methyl)-phenyl]-amine), was synthesized and fully characterized by 1H-NMR, MALDI-TOF-MS spectra and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1, with a=11.827(1), b=16.000(2), c=16.527(2)Å, α=108.510(1), β=91.116(5), γ=101.734(1)°, V=2894.5(6)Å3, Z=1, Dc=1.262 g/m3, F(000)=1162, Mr=545.63, μ=0.083 mm-1 , the final R=0.0728 and wR=0.2213 for 7541 observed reflections with I>2σ(I). The structural analysis revealed that three pyrazole units are attached to the same carbon atom connected with bis-(4-ethoxy-phenyl)-phenyl-amine group. UV-vis spectral features of the ligand in various solutions were explained by time dependent density functional theory (TD-DFT). It was also found that the ligand (BTA) exhibits an exclusively selective and sensitive response toward Fe3+ using UV-vis spectroscopic method.
2014, 33(11): 1580-1586
doi: 10.14102/j.cnki.0254-5861.2011-0310
Abstract:
One complex [Co1.5(C6H5CHCHCOO)3(Medpq)]·H2O (C6H5CHCHCOO=cinnamic acid, Medpq=2-methyldipyrido[3,2-f:2',3'-h]quinoxaline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG, single-crystal X-ray diffraction and magnetic susceptibility measurements. Complex 1 crystallizes in the triclinic system, space group P1, with a=10.224(5), b=14.572(5), c=15.139(5)Å, α=112.704(5), β=97.168(5), γ=109.749(5), V=1871.8(13)Å3 and Z=2 (at 293(2) K). In the crystal structure, the Co(1) ion is hexa-coordinated with six atoms from three different cinnamic acid ligands and the symmetric three different cinnamic acid ligands; the Co(2) center adopts a coordination environment with two nitrogen atoms from Medpq ligand and four oxygen atoms from two different cinnamic ligands, assuming a slightly distorted octahedral geometry, respectively. The negative value of the Weiss constant indicates antiferromagnetic exchange interactions between the Co ions.
One complex [Co1.5(C6H5CHCHCOO)3(Medpq)]·H2O (C6H5CHCHCOO=cinnamic acid, Medpq=2-methyldipyrido[3,2-f:2',3'-h]quinoxaline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG, single-crystal X-ray diffraction and magnetic susceptibility measurements. Complex 1 crystallizes in the triclinic system, space group P1, with a=10.224(5), b=14.572(5), c=15.139(5)Å, α=112.704(5), β=97.168(5), γ=109.749(5), V=1871.8(13)Å3 and Z=2 (at 293(2) K). In the crystal structure, the Co(1) ion is hexa-coordinated with six atoms from three different cinnamic acid ligands and the symmetric three different cinnamic acid ligands; the Co(2) center adopts a coordination environment with two nitrogen atoms from Medpq ligand and four oxygen atoms from two different cinnamic ligands, assuming a slightly distorted octahedral geometry, respectively. The negative value of the Weiss constant indicates antiferromagnetic exchange interactions between the Co ions.
2014, 33(11): 1587-1592
doi: 10.14102/j.cnki.0254-5861.2011-0282
Abstract:
A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n (1, L1=4'-(4-pyridyl)-4,2':6',4"-terpyridine, 5-nipc=5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a=29.983(9), b=13.709(3), c=14.391(3)Å, β=114.93(4)°, V=5364(2)Å3, Dc=1.493 g/cm3, C28H19N5O7Zn, Mr=602.85, F(000)=2464, μ(MoKα)=0.972 mm-1, Z=8, R=0.0935 and wR=0.1509 for 4724 observed reflections (I>2σ(I)). The structure of 1 exhibits a three-dimensional (3D) network with a layer-pillar structure. The fluorescence property of 1 is also investigated.
A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n (1, L1=4'-(4-pyridyl)-4,2':6',4"-terpyridine, 5-nipc=5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a=29.983(9), b=13.709(3), c=14.391(3)Å, β=114.93(4)°, V=5364(2)Å3, Dc=1.493 g/cm3, C28H19N5O7Zn, Mr=602.85, F(000)=2464, μ(MoKα)=0.972 mm-1, Z=8, R=0.0935 and wR=0.1509 for 4724 observed reflections (I>2σ(I)). The structure of 1 exhibits a three-dimensional (3D) network with a layer-pillar structure. The fluorescence property of 1 is also investigated.
2014, 33(11): 1593-1596
doi: 10.14102/j.cnki.0254-5861.2011-0313
Abstract:
A novel silver(Ⅰ) complex [Ag(2,2'-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a=27.4089(13), b=10.2897(5), c=12.0024(6)Å, β=111.864(4)°, Mr=715.49, V=3141.5(3)Å3, Dc=1.513 g/cm3, Z=4, μ(MoKα)=0.694 mm-1, F(000)=1456, the final R=0.0473 and wR=0.1146. In the title complex, the central Ag(Ⅰ) ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495~520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.
A novel silver(Ⅰ) complex [Ag(2,2'-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a=27.4089(13), b=10.2897(5), c=12.0024(6)Å, β=111.864(4)°, Mr=715.49, V=3141.5(3)Å3, Dc=1.513 g/cm3, Z=4, μ(MoKα)=0.694 mm-1, F(000)=1456, the final R=0.0473 and wR=0.1146. In the title complex, the central Ag(Ⅰ) ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495~520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.
2014, 33(11): 1597-1602
doi: 10.14102/j.cnki.0254-5861.2011-0315
Abstract:
A new luminescent coordination polymer [Zn(tdc)(pbim)]n 1 (tdc=3,4-thiophenedicarboxylate, pbim=1,3-bis(benzimidazol-1'-yl)propane) has been synthesized under hydrothermal conditions. The compound crystallizes in monoclinic system, space group P21/c with a=8.4840(9), b=16.4913(17), c=14.9234(16)Å, β=95.8870(10)°, V=2077.0(4)Å3, Z=4, Mr=511.84, Dc=1.637 Mg/m3, μ=1.324 mm-1, F(000)=1048, the final R=0.0361 and wR=0.0824 for 3656 observed reflections with I>2σ(I). Structural analyses reveal that 1 exhibits a onedimensional (1D) double chain, which is further connected into a two-dimensional (2D) supramolecular architecture by π-π stacking interactions. The results indicate that H2tdc and pbim ligand are effective building blocks in constructing polymers with diverse architecture. Solid state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.
A new luminescent coordination polymer [Zn(tdc)(pbim)]n 1 (tdc=3,4-thiophenedicarboxylate, pbim=1,3-bis(benzimidazol-1'-yl)propane) has been synthesized under hydrothermal conditions. The compound crystallizes in monoclinic system, space group P21/c with a=8.4840(9), b=16.4913(17), c=14.9234(16)Å, β=95.8870(10)°, V=2077.0(4)Å3, Z=4, Mr=511.84, Dc=1.637 Mg/m3, μ=1.324 mm-1, F(000)=1048, the final R=0.0361 and wR=0.0824 for 3656 observed reflections with I>2σ(I). Structural analyses reveal that 1 exhibits a onedimensional (1D) double chain, which is further connected into a two-dimensional (2D) supramolecular architecture by π-π stacking interactions. The results indicate that H2tdc and pbim ligand are effective building blocks in constructing polymers with diverse architecture. Solid state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.
2014, 33(11): 1603-1609
doi: 10.14102/j.cnki.0254-5861.2011-0339
Abstract:
One new coordination polymer, [Ni(m-bix)(m-BDC)] (1, m-bix=1,3-bis(imidazol-1-ylmethyl)benzene, m-BDC=1,3-benzenedicarboxylic acids), has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The green block crystal of complex 1 (C22H18N4NiO4) belongs to monoclinic system, space group P21/c with a=10.0418(3), b=23.8651(6), c=8.7872(2)Å, β=112.333(3)°, V=1947.88(9)Å3, Z=4, Dc=1.572 g/cm3, Mr=461.11, F(000)=952, R=0.0335 and wR=0.0683 for 2827 observed reflections (I>2σ(I)). Complex 1 exhibits a novel 6-connected 3D sxd type topological framework. The magnetic characterization of complex 1 shows antiferromagnetic coupling exchange.
One new coordination polymer, [Ni(m-bix)(m-BDC)] (1, m-bix=1,3-bis(imidazol-1-ylmethyl)benzene, m-BDC=1,3-benzenedicarboxylic acids), has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The green block crystal of complex 1 (C22H18N4NiO4) belongs to monoclinic system, space group P21/c with a=10.0418(3), b=23.8651(6), c=8.7872(2)Å, β=112.333(3)°, V=1947.88(9)Å3, Z=4, Dc=1.572 g/cm3, Mr=461.11, F(000)=952, R=0.0335 and wR=0.0683 for 2827 observed reflections (I>2σ(I)). Complex 1 exhibits a novel 6-connected 3D sxd type topological framework. The magnetic characterization of complex 1 shows antiferromagnetic coupling exchange.
2014, 33(11): 1610-1616
doi: 10.14102/j.cnki.0254-5861.2011-0325
Abstract:
Reaction of a N-heterocycliccarbene (NHC) containing an anthracene unit and two N-picolyl moieties with Hg(OAc)2 yielded a novel mercury(Ⅱ) complex (1). X-ray studies, UV-vis and fluorescence spectroscopy confirmed that a strong interaction exists between the mercury atom and anthracene unit.
Reaction of a N-heterocycliccarbene (NHC) containing an anthracene unit and two N-picolyl moieties with Hg(OAc)2 yielded a novel mercury(Ⅱ) complex (1). X-ray studies, UV-vis and fluorescence spectroscopy confirmed that a strong interaction exists between the mercury atom and anthracene unit.
2014, 33(11): 1617-1622
doi: 10.14102/j.cnki.0254-5861.2011-0320
Abstract:
A new porous Cd(Ⅱ) coordination compound, namely, [Cd(bpdc)(L)2]·3H2O (1, L=11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine and bpdc=1,1'-biphenyl-2,2'-dicarboxylate) was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffraction. It crystallizes in tetragonal, space group P4122 with a=9.8486(4), b=9.8486(4), c=45.925(4)Å, V=4454.5(5)Å3, Z=4, C50H29CdF2N8O7, Mr=1004.21, Dc=1.497 g/cm3, F(000)=2028, μ(MoKa)=0.562 mm-1, R=0.0566 and wR=0.1585. Each Cd(Ⅱ) atom is coordinated by one bpdc anion and two L ligands to give a discrete molecule. Neighboring discrete molecules are stacked by π-π interactions among L ligands, resulting in an interesting 1D supramolecular chain. Moreover, the 1D supramolecular chains are packed with each other to give a porous structure, in which an infinite channel is filled with water molecules. In addition, the thermal behavior and luminescent property of 1 have also been studied.
A new porous Cd(Ⅱ) coordination compound, namely, [Cd(bpdc)(L)2]·3H2O (1, L=11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine and bpdc=1,1'-biphenyl-2,2'-dicarboxylate) was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffraction. It crystallizes in tetragonal, space group P4122 with a=9.8486(4), b=9.8486(4), c=45.925(4)Å, V=4454.5(5)Å3, Z=4, C50H29CdF2N8O7, Mr=1004.21, Dc=1.497 g/cm3, F(000)=2028, μ(MoKa)=0.562 mm-1, R=0.0566 and wR=0.1585. Each Cd(Ⅱ) atom is coordinated by one bpdc anion and two L ligands to give a discrete molecule. Neighboring discrete molecules are stacked by π-π interactions among L ligands, resulting in an interesting 1D supramolecular chain. Moreover, the 1D supramolecular chains are packed with each other to give a porous structure, in which an infinite channel is filled with water molecules. In addition, the thermal behavior and luminescent property of 1 have also been studied.
2014, 33(11): 1623-1628
doi: 10.14102/j.cnki.0254-5861.2011-0326
Abstract:
Two new coordination complexes, [Pr(1,3-pda)0.5(nbca)2(H2O)2] (1) and [Pr2(1,3-pda)3(2,2'-bpy)2(H2O)2] (2) (H2pda=1,3-phenylenediacetic acid, Hnbca=5-nitro [1,1'-biphenyl]-3-carboxylic acid, 2,2'-bpy=2,2'-bipyridine), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In 1, the nbca ligands bridge the Pr3+ ions to form a 1D chain. Moreover, these 1D chains are united together through the 1,3-pda ligands to afford a 2D layer. In contrast, due to a different auxiliary ligand, complex 2 is a 2D layer linked through only bridging deprotonated 1,3-pda. Thermal stabilities and solid fluorescence properties of 1 and 2 were also studied.
Two new coordination complexes, [Pr(1,3-pda)0.5(nbca)2(H2O)2] (1) and [Pr2(1,3-pda)3(2,2'-bpy)2(H2O)2] (2) (H2pda=1,3-phenylenediacetic acid, Hnbca=5-nitro [1,1'-biphenyl]-3-carboxylic acid, 2,2'-bpy=2,2'-bipyridine), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In 1, the nbca ligands bridge the Pr3+ ions to form a 1D chain. Moreover, these 1D chains are united together through the 1,3-pda ligands to afford a 2D layer. In contrast, due to a different auxiliary ligand, complex 2 is a 2D layer linked through only bridging deprotonated 1,3-pda. Thermal stabilities and solid fluorescence properties of 1 and 2 were also studied.
2014, 33(11): 1629-1635
doi: 10.14102/j.cnki.0254-5861.2011-0328
Abstract:
Two new metal-organic coordination polymers [Co0.5(Heoba)(bib)0.5]2n (1) and [Cd(eoba)(phen)]n (2) (H2eoba=4,4'-(ethane-1,2-diyldioxy)dibenzoic acid, bib>=1,4-bis (imidazol-1-yl)-butane, phen=1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. Complex 1 is a 2D network structure, and complex 2 exhibits a 3D network structure. Moreover, the luminescent property of complex 2 has been investigated in the solid state.
Two new metal-organic coordination polymers [Co0.5(Heoba)(bib)0.5]2n (1) and [Cd(eoba)(phen)]n (2) (H2eoba=4,4'-(ethane-1,2-diyldioxy)dibenzoic acid, bib>=1,4-bis (imidazol-1-yl)-butane, phen=1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. Complex 1 is a 2D network structure, and complex 2 exhibits a 3D network structure. Moreover, the luminescent property of complex 2 has been investigated in the solid state.
2014, 33(11): 1636-1642
doi: 10.14102/j.cnki.0254-5861.2011-0345
Abstract:
A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n (1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a=12.060(4), b=8.493(3), c=15.776(5) (Å), β=93.235(3)°, V=1613.4(9)Å3, Z=4, Mr=730.12, Dc=3.006 Mg/m3, μ=6.581 mm-1, F(000)=1368, the final R=0.0283 and wR=0.0866 for 2939 observed reflections with I>2σ(I). Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.
A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n (1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a=12.060(4), b=8.493(3), c=15.776(5) (Å), β=93.235(3)°, V=1613.4(9)Å3, Z=4, Mr=730.12, Dc=3.006 Mg/m3, μ=6.581 mm-1, F(000)=1368, the final R=0.0283 and wR=0.0866 for 2939 observed reflections with I>2σ(I). Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.
2014, 33(11): 1643-1648
doi: 10.14102/j.cnki.0254-5861.2011-0352
Abstract:
The tridentate ligand DPA-Me (2) was readily prepared from DPA (DPA=2,2'-dipicolylamine) in high yield. The mixture of 2 and Cu(ClO4)2·6H2O in methanol gave a five-coordinated mononuclear complex [(DPA-Me)Cu(MeCN)(ClO4)](ClO4) (3). Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu(DPA-Me)]2(CN)(ClO4)3·CH3NO2}n (4). Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a=17.74582(15), b=13.89877(11), c=14.92546(13)Å, β=91.4246(8)°, V=3680.15(5)Å3, Z=4, Dc=1.695 g/cm3, F(000)=1912, C28H33Cl3Cu2N8O14, Mr=939.05, μ=1.602 cm-1, CuKα radiation (λ=1.54184Å), R=0.0485 and wR=0.1246 for 6414 observed reflections with I>2σ(I).
The tridentate ligand DPA-Me (2) was readily prepared from DPA (DPA=2,2'-dipicolylamine) in high yield. The mixture of 2 and Cu(ClO4)2·6H2O in methanol gave a five-coordinated mononuclear complex [(DPA-Me)Cu(MeCN)(ClO4)](ClO4) (3). Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu(DPA-Me)]2(CN)(ClO4)3·CH3NO2}n (4). Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a=17.74582(15), b=13.89877(11), c=14.92546(13)Å, β=91.4246(8)°, V=3680.15(5)Å3, Z=4, Dc=1.695 g/cm3, F(000)=1912, C28H33Cl3Cu2N8O14, Mr=939.05, μ=1.602 cm-1, CuKα radiation (λ=1.54184Å), R=0.0485 and wR=0.1246 for 6414 observed reflections with I>2σ(I).
2014, 33(11): 1649-1654
doi: 10.14102/j.cnki.0254-5861.2011-0372
Abstract:
A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O (1, H2ox=oxalic acid, H2pydc=pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assembly of lanthanide ions (Eu3+) with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1, with a=11.225(4), b=12.390(5), c=13.752(5)Å, α=89.228(7), β=71.142(6), γ=75.552(6)°, Dc=2.317 g/cm3, μ=5.480 mm-1, F(000)=1150, Z=2, the final R=0.0351 and wR=0.0949 for 8782 observed reflections with I>2σ(I). Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0→7F2 transition of Eu3+ ions.
A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O (1, H2ox=oxalic acid, H2pydc=pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assembly of lanthanide ions (Eu3+) with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1, with a=11.225(4), b=12.390(5), c=13.752(5)Å, α=89.228(7), β=71.142(6), γ=75.552(6)°, Dc=2.317 g/cm3, μ=5.480 mm-1, F(000)=1150, Z=2, the final R=0.0351 and wR=0.0949 for 8782 observed reflections with I>2σ(I). Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0→7F2 transition of Eu3+ ions.
2014, 33(11): 1655-1660
doi: 10.14102/j.cnki.0254-5861.2011-435
Abstract:
Two novel L-amino alcohol coordination cobalt and copper complexes Ⅰ and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co(Ⅱ) acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu(Ⅱ) chloride dihydrate in anhydrous methanol. The structures of Ⅰ and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For Ⅰ: [Co3(C51H66N3O16)]2(OAc), monoclinic, space group P21, a=15.022(3), b=14.242(3), c=28.922(6)Å, β=98.944(4)°, V=6112(2)Å3, Z=4, Dc=1.339 g/cm3, the final R=0.0860 for 21906 observed reflections with I>2σ(I). For Ⅱ: Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a=6.1861(13), b=20.838(4), c=28.274(6)Å, V=3644.6(13)Å3, Z=4, Dc=1.310 g/cm3, the final R=0.0642 for 11106 observed reflections with I>2σ(I). The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.
Two novel L-amino alcohol coordination cobalt and copper complexes Ⅰ and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co(Ⅱ) acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu(Ⅱ) chloride dihydrate in anhydrous methanol. The structures of Ⅰ and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For Ⅰ: [Co3(C51H66N3O16)]2(OAc), monoclinic, space group P21, a=15.022(3), b=14.242(3), c=28.922(6)Å, β=98.944(4)°, V=6112(2)Å3, Z=4, Dc=1.339 g/cm3, the final R=0.0860 for 21906 observed reflections with I>2σ(I). For Ⅱ: Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a=6.1861(13), b=20.838(4), c=28.274(6)Å, V=3644.6(13)Å3, Z=4, Dc=1.310 g/cm3, the final R=0.0642 for 11106 observed reflections with I>2σ(I). The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.
2014, 33(11): 1661-1665
doi: 10.14102/j.cnki.0254-5861.2011-0354
Abstract:
A three-coordinate Ag(Ⅰ) complex, [Ag(Mepzpy)(PAr3)]BF4·H2O (1, Mepzpy=3-methyl-1-(2-pyridyl)pyrazole, PAr3=tri(o-tolyl)phosphine), was synthesized from the reaction of Ag(CH3CN)4BF4, PAr3 and Mepzpy in CH3CN at room temperature. The compound was characterized by UV-vis, NMR and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1, with a=10.2251(5), b=10.6014(5), c=15.7012(5)Å, α=92.963(3), β=92.641(3), γ=114.647(4)°, V=1540.6(1)Å3, Z=2, Mr=676.24, Dc=1.458 g/cm3, F(000)=688, μ=6.187 mm-1, GOOF=1.038, the final R=0.0530 and wR=0.1493 for 6371 observed reflections with I>2σ(I). Compound 1 is ionic. It is composed of a BF4- anion and a [Ag(Mepzpy)(PAr3)]+ cation. The Ag(Ⅰ) ion adopts a distorted trigonal pyramidal coordination geometry defined by two nitrogen atoms and a phosphorous atom. The complex emits blue luminescence with maximum peaks at 470 nm in solid state at room temperature.
A three-coordinate Ag(Ⅰ) complex, [Ag(Mepzpy)(PAr3)]BF4·H2O (1, Mepzpy=3-methyl-1-(2-pyridyl)pyrazole, PAr3=tri(o-tolyl)phosphine), was synthesized from the reaction of Ag(CH3CN)4BF4, PAr3 and Mepzpy in CH3CN at room temperature. The compound was characterized by UV-vis, NMR and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1, with a=10.2251(5), b=10.6014(5), c=15.7012(5)Å, α=92.963(3), β=92.641(3), γ=114.647(4)°, V=1540.6(1)Å3, Z=2, Mr=676.24, Dc=1.458 g/cm3, F(000)=688, μ=6.187 mm-1, GOOF=1.038, the final R=0.0530 and wR=0.1493 for 6371 observed reflections with I>2σ(I). Compound 1 is ionic. It is composed of a BF4- anion and a [Ag(Mepzpy)(PAr3)]+ cation. The Ag(Ⅰ) ion adopts a distorted trigonal pyramidal coordination geometry defined by two nitrogen atoms and a phosphorous atom. The complex emits blue luminescence with maximum peaks at 470 nm in solid state at room temperature.
2014, 33(11): 1666-1672
doi: 10.14102/j.cnki.0254-5861.2011-0370
Abstract:
A novel 1,4,5-trisubstituted 1,2,3-triazole (C18H21N3O3) was synthesized by a one-pot three component reaction of 1-azidocyclohexane, 1-copper(Ⅰ) phenylethyne and ethoxalyl chloride at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P21/n with a=12.8167(9), b=8.0966(6), c=16.7079(9)Å, β=98.716(2)°, Z=4 and V=1713.8(2). In the crystal, the molecules are related by inversion and paired into dimers via C-H…O and C-O…C interactions involving (oxo) acetate groups. Furthermore, X-ray analysis results are compared with the optimized structure computed by using B3LYP method with 6-311G basis set. The calculated results showed that optimized geometry can well reproduce the crystal structure parameters. The bioassay results indicate that the compound has good antibacterial and antifungal activities.
A novel 1,4,5-trisubstituted 1,2,3-triazole (C18H21N3O3) was synthesized by a one-pot three component reaction of 1-azidocyclohexane, 1-copper(Ⅰ) phenylethyne and ethoxalyl chloride at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P21/n with a=12.8167(9), b=8.0966(6), c=16.7079(9)Å, β=98.716(2)°, Z=4 and V=1713.8(2). In the crystal, the molecules are related by inversion and paired into dimers via C-H…O and C-O…C interactions involving (oxo) acetate groups. Furthermore, X-ray analysis results are compared with the optimized structure computed by using B3LYP method with 6-311G basis set. The calculated results showed that optimized geometry can well reproduce the crystal structure parameters. The bioassay results indicate that the compound has good antibacterial and antifungal activities.
2014, 33(11): 1673-1682
doi: 10.14102/j.cnki.0254-5861.2011-0367
Abstract:
A series of novel α-aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified by IR, 1H NMR, 13C NMR and elemental analysis. The crystal structure of diethyl[(4-cyano-1H-pyrazol-3-ylamino)(3,5-difluorophenyl)methyl]phosphonate (4a, C15H17F2N4O3P) was determined by single-crystal X-ray diffraction. Compound 4a crystallizes in the triclinic system, space group P1, with a=8.381(3), b=10.103(5), c=11.268(3)Å, α=83.772(19), β=74.726(19), γ=70.964(18)°, V=869.9(6)Å3, Mr=370.30, Dc=1.414 g/cm3, Z=2, F(000)=384, μ=0.200 mm-1, MoKa radiation (λ=0.71073Å), the final R=0.0487 and wR=0.0823 for 1582 observed reflections with I>2σ(I). X-ray diffraction analysis reveals that there are two planes in 4a, and the dihedral angle is 71.51°. Two intermolecular hydrogen bonds and a face-to-face π…π stacking interaction are observed in the crystal structure. The compounds were evaluated for their antifungal, antiviral and antitumor activities, respectively. Among them, 4b, 4c, 4g and 4h exhibit good activities on Sclerotium rolfsii Sacc at 200 μg/mL, while 4b, 4c, 4f and 4g possess good anti-TMV activities at 500 μg/mL. Unfortunately, all of the compounds showed weak antitumor activities.
A series of novel α-aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified by IR, 1H NMR, 13C NMR and elemental analysis. The crystal structure of diethyl[(4-cyano-1H-pyrazol-3-ylamino)(3,5-difluorophenyl)methyl]phosphonate (4a, C15H17F2N4O3P) was determined by single-crystal X-ray diffraction. Compound 4a crystallizes in the triclinic system, space group P1, with a=8.381(3), b=10.103(5), c=11.268(3)Å, α=83.772(19), β=74.726(19), γ=70.964(18)°, V=869.9(6)Å3, Mr=370.30, Dc=1.414 g/cm3, Z=2, F(000)=384, μ=0.200 mm-1, MoKa radiation (λ=0.71073Å), the final R=0.0487 and wR=0.0823 for 1582 observed reflections with I>2σ(I). X-ray diffraction analysis reveals that there are two planes in 4a, and the dihedral angle is 71.51°. Two intermolecular hydrogen bonds and a face-to-face π…π stacking interaction are observed in the crystal structure. The compounds were evaluated for their antifungal, antiviral and antitumor activities, respectively. Among them, 4b, 4c, 4g and 4h exhibit good activities on Sclerotium rolfsii Sacc at 200 μg/mL, while 4b, 4c, 4f and 4g possess good anti-TMV activities at 500 μg/mL. Unfortunately, all of the compounds showed weak antitumor activities.
2014, 33(11): 1683-1688
doi: 10.14102/j.cnki.0254-5861.2011-0350
Abstract:
Compound (Z)-2-methyl-5,6-dihydrobenzo[d]thiazol-7(4H)-one O-prop-2-yn-1-yl oxime, C11H12N2OS, as a synthetic precursor of cytotoxic triazoles has been prepared and characterized by NMR spectra. Meanwhile, the crystal of Ⅳ was obtained and determined by X-ray single-crystal diffraction. Crystal data: monoclinic system, space group P21/c, a=9.725(9), b=8.068(7), c=14.452(13)Å, β=98.68(2)°, V=1120.9(17)Å3, Z=4, F(000)=464, Dc=1.305 g/cm3, μ=0.263 mm-1, R=0.0457 and wR=0.1298 for 11511 independent reflections (Rint=0.0709) and 2289 observed ones (I>2σ(I)).
Compound (Z)-2-methyl-5,6-dihydrobenzo[d]thiazol-7(4H)-one O-prop-2-yn-1-yl oxime, C11H12N2OS, as a synthetic precursor of cytotoxic triazoles has been prepared and characterized by NMR spectra. Meanwhile, the crystal of Ⅳ was obtained and determined by X-ray single-crystal diffraction. Crystal data: monoclinic system, space group P21/c, a=9.725(9), b=8.068(7), c=14.452(13)Å, β=98.68(2)°, V=1120.9(17)Å3, Z=4, F(000)=464, Dc=1.305 g/cm3, μ=0.263 mm-1, R=0.0457 and wR=0.1298 for 11511 independent reflections (Rint=0.0709) and 2289 observed ones (I>2σ(I)).
2014, 33(11): 1689-1696
doi: 10.14102/j.cnki.0254-5861.2011-0466
Abstract:
A new inorganic-organic hybrid constructed from biisoquinoline dication and tin halide, [(BIQBT)(SnCl6)]n (1, BIQBT=1,4-bis(isoquinoline) butane), has been synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in the monoclinic system, space group Cc with Mr=644.82, a=16.589(3), b=18.388(4), c=8.5532(17)Å, β=108.75(3)°, V=2470.6(9)Å3, Z=4, Dc=1.736 g/cm3, F(000)=1281, μ(MoKα)=1.697 mm-1, the final R=0.0197 and wR=0.0493 for 4614 observed reflections with I>2σ(I). 1 consists of BIQBT2+ dications and mononuclear hexachloridostannate SnCl62- anion, and hydrogen bonds among them contribute to the formation of a 1-D chain. Strong fluorescence can be detected in 1, which was explained by theoretical calculation. Its electrochemical behavior was investigated, and the theoretical calculations reveal that the π…π stacking interaction is dominated for their structural stabilization.
A new inorganic-organic hybrid constructed from biisoquinoline dication and tin halide, [(BIQBT)(SnCl6)]n (1, BIQBT=1,4-bis(isoquinoline) butane), has been synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in the monoclinic system, space group Cc with Mr=644.82, a=16.589(3), b=18.388(4), c=8.5532(17)Å, β=108.75(3)°, V=2470.6(9)Å3, Z=4, Dc=1.736 g/cm3, F(000)=1281, μ(MoKα)=1.697 mm-1, the final R=0.0197 and wR=0.0493 for 4614 observed reflections with I>2σ(I). 1 consists of BIQBT2+ dications and mononuclear hexachloridostannate SnCl62- anion, and hydrogen bonds among them contribute to the formation of a 1-D chain. Strong fluorescence can be detected in 1, which was explained by theoretical calculation. Its electrochemical behavior was investigated, and the theoretical calculations reveal that the π…π stacking interaction is dominated for their structural stabilization.
2014, 33(11): 1697-1702
doi: 10.14102/j.cnki.0254-5861.2011-0341
Abstract:
A new mixed-valence heterometal cluster Mo8ⅤW2ⅥO26(C5H5N)8·2H2O has been synthesized under solvothermal conditions and characterized by X-ray single-crystal diffraction, IR, UV-vis and XPS spectroscopy. The title compound crystallizes in the triclinic system, space group P1, with a=11.708(3), b=12.018(4), c=13.316(4)Å, α=112.184(4), β=97.844(4), γ=110.043(3)°, V=1551.9(8)Å3 and Z=1 at 293(2) K. The final full-matrix least-squares refinement converged to R=0.0414 for 4460 observed unique reflections with I>2σ(I) and wR=0.1290 for all data (5352) and S=1.015. In addition, its thermal stability and fluorescent property have also been investigated.
A new mixed-valence heterometal cluster Mo8ⅤW2ⅥO26(C5H5N)8·2H2O has been synthesized under solvothermal conditions and characterized by X-ray single-crystal diffraction, IR, UV-vis and XPS spectroscopy. The title compound crystallizes in the triclinic system, space group P1, with a=11.708(3), b=12.018(4), c=13.316(4)Å, α=112.184(4), β=97.844(4), γ=110.043(3)°, V=1551.9(8)Å3 and Z=1 at 293(2) K. The final full-matrix least-squares refinement converged to R=0.0414 for 4460 observed unique reflections with I>2σ(I) and wR=0.1290 for all data (5352) and S=1.015. In addition, its thermal stability and fluorescent property have also been investigated.
2014, 33(11): 1703-1712
doi: 10.14102/j.cnki.0254-5861.2011-0353
Abstract:
Hydrothermal reactions of Na2MoO2·2H2O and NH4VO3 (or V2O5) with appropriate reducing agents such as organic amines, NH2OH·HCl and Mo(CO)6 gave rise to the formation of a series of capped Keggin derivatives, [N(CH3)4]2Na3(NH4)2[(VⅤO4)Mo8ⅥV4ⅣO36(VⅣO)2]·13H2O (1), [NH4]7[(VⅤO4)Mo8ⅥV4ⅣO36(VⅣO)2]·7H2O (2), [HN(CH2CH2)3NH][(PO4)Mo3ⅤMo9ⅥO36(VⅣO)2]·3[N(CH2CH2)3N]·(en)·4.5H2O (3) and [HNH2OH][NH4]2[(VⅤO4)Mo8ⅥV4ⅣO36(VⅣO)4]·24H2O (4). Single-crystal X-ray diffraction analysis revealed that the anions in 1~3 are two-capped Keggin derivatives with characteristic trans vanadium-oxygen caps, whereas the heteropoly anion in 4 is a tetra-capped α-Keggin derivative with characteristic vanadium-oxygen caps on the equatorial plane.
Hydrothermal reactions of Na2MoO2·2H2O and NH4VO3 (or V2O5) with appropriate reducing agents such as organic amines, NH2OH·HCl and Mo(CO)6 gave rise to the formation of a series of capped Keggin derivatives, [N(CH3)4]2Na3(NH4)2[(VⅤO4)Mo8ⅥV4ⅣO36(VⅣO)2]·13H2O (1), [NH4]7[(VⅤO4)Mo8ⅥV4ⅣO36(VⅣO)2]·7H2O (2), [HN(CH2CH2)3NH][(PO4)Mo3ⅤMo9ⅥO36(VⅣO)2]·3[N(CH2CH2)3N]·(en)·4.5H2O (3) and [HNH2OH][NH4]2[(VⅤO4)Mo8ⅥV4ⅣO36(VⅣO)4]·24H2O (4). Single-crystal X-ray diffraction analysis revealed that the anions in 1~3 are two-capped Keggin derivatives with characteristic trans vanadium-oxygen caps, whereas the heteropoly anion in 4 is a tetra-capped α-Keggin derivative with characteristic vanadium-oxygen caps on the equatorial plane.
2014, 33(11): 1713-1721
doi: 10.14102/j.cnki.0254-5861.2011-0340
Abstract:
Two coordination polymers, namely [Co(5-Clnic)2(H2biim)]n 1 and {[Ni(5-Clnic)(Hbiim)]·H2O}n 2 (5-ClnicH=5-halonicotinic acid, H2biim=2,2'-biimidazole), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N-H…O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N-H…O and O-H…O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.
Two coordination polymers, namely [Co(5-Clnic)2(H2biim)]n 1 and {[Ni(5-Clnic)(Hbiim)]·H2O}n 2 (5-ClnicH=5-halonicotinic acid, H2biim=2,2'-biimidazole), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N-H…O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N-H…O and O-H…O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.
