The two complexes [Cu(C5H2N2O4)(H2O)3]·2H2O (1) and [Ni(C5H2N2O4)(H2O)4]·H2O (2) were synthesized by self assembly reactions of Cu(NO3)2·3H2O or Ni(CH3COO)2·4H2O with orotic acid (2,6 dioxo 1,2,3,6...The two complexes [Cu(C5H2N2O4)(H2O)3]·2H2O (1) and [Ni(C5H2N2O4)(H2O)4]·H2O (2) were synthesized by self assembly reactions of Cu(NO3)2·3H2O or Ni(CH3COO)2·4H2O with orotic acid (2,6 dioxo 1,2,3,6 tetrahydro 4 pyrimidinecarboxylic acid), respectively. Their crystal structures were determined by single crystal X ray diffraction analyses. Crystallographic data for complex 1: C5H8N2CuO7·2H2O, Mr=307.7, monoclinic P21/n, a=0.57710(1)nm, b=1.76863(6)nm, c=1.09955(4)nm, β=98.600(2)°, V=1.109.63(6)nm3, Z=4 , Dc=1.842g·cm-3, μ(MoKα)=2.010mm-1, F(000)=628, R=0.0436, wR=0.1015, And for complex 2: C5H10N2NiO8·H2O, Mr=302.88, orthorhombic Pbcn, a=2.0763(1)nm, b=1.69355(9)nm, c=0.73478(4)nm, V=2.5837(2)nm3, Z=8, Dc=1.557g·cm-3, μ(MoKα)=1.538 mm-1, F(000)=1248, R=0.0545, wR=0.1305. The X ray analyses revealed that the Cu? and Ni? atoms are both coordinated by carboxylic O atom and contiguous N atom of the pyrimidine ring. In complex 1 the Cu? atom has a slightly distorted square pyramid coordination environment with additional three water molecules, while in complex 2 the Ni? atom adopts a slightly distorted octahedral geometry with additional four water molecules. The three dimensional frameworks of the two complexes are formed by intermolecular hydrogen bonding interactions. CCDC: 1, 204881; 2, 204882.展开更多
The title complex was prepared from self-assembly reaction of La（NO3）3(6H2O, Zn（NO3）2(6H2O, m-cyanobenzoic acid （m-CNC6H4COOH） and pyridine （Py） in refluxing ethanol and its structure was determined by single-...The title complex was prepared from self-assembly reaction of La（NO3）3(6H2O, Zn（NO3）2(6H2O, m-cyanobenzoic acid （m-CNC6H4COOH） and pyridine （Py） in refluxing ethanol and its structure was determined by single-crystal X-ray diffraction. Crystallographic data: C94H62N12La2O22Zn2, Mr = 2120.12, triclinic space group P, a = 13.2219（5）, b = 13.2713（5）, c = 14.1987（6） ?, (???69.156（1）, ( = 84.034（1）, ( = 89.400（1） (, V = 2314.9（2） ?3, Z = 1, Dc = 1.521 g/cm3, F（000） = 1060, ( (MoK（） = 14.94 cm－1, the final R = 0.043 and wR = 0.117 for 6381 unique reflections with I > 2(（I）. Crystal structure determination shows that the neighboring lanthanum（III） and zinc（II） ions are bridged by three bidentate m-cyanobenzonate ligands in the syn-syn fashion to form a pair of dinuclear [LaZn（m-CNC6H4COO）3（Py）（C2H5OH）] subunits, being linked together by two bidentate and two tridentate m-cyanobenzonate groups in the syn-syn and syn-anti modes, respectively, to construct a tetranuclear La-Zn complex [La2Zn2（m-CNC6H4COO）10（Py）2（C2H5OH）2].展开更多
A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-cr...A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.展开更多
The title compound (C_ 24H_ 40Cl_6O_ 16V_3, M_r = 950.08) was synthesized from the reaction of VCl_3 and NaO_2CEt in CHCl_3 and THF. The crystal structure has been determined by X-ray single-crystal diffraction ana...The title compound (C_ 24H_ 40Cl_6O_ 16V_3, M_r = 950.08) was synthesized from the reaction of VCl_3 and NaO_2CEt in CHCl_3 and THF. The crystal structure has been determined by X-ray single-crystal diffraction analysis. It crystallizes in monoclinic space group C2/c with a = 12.5768(4), b= 16.5601(4), c = 19.3574(7) , β = 99.879(1)°, V = 3971.3(2)3, D_c = 1.589 g/cm3, μ= 1.157 mm -1, F(000)=1932, Z=4, R = 0.055, wR = 0.1539 (I2σ(I)). This compound has an unusual coplanar V_3O core with a C_2 axis passing through O(1), V(1), O(10): one V-μ_3O is short (1.628 ), the other two are longer (2.381 ). It was characterized by IR, 1H NMR, and EPR spectra. It was unstable and the decomposition process of this compound was studied using IR spectroscopy.展开更多
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det...The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.展开更多
A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform...A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra（FTIR）, circular dichroism（CD） and thermogravimetric analyses（TGA）. Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.展开更多
A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solut...A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C72H40N10O12Tb2, Mr=1554.98, triclinic Pi, a = 9.903（3）, b = 11.769（8）, c = 15.078（8）A, a = 111.42（12）, It = 96.37（19）, γ = 101-24（14）°, V= 1572（1）A3, Z= 1, Dc = 1.642 g/cm^3, F（000） = 768 μ = 2.305 mm^-1, the final R = 0.0205 and wR = 0.0543 for 5479 reflections with I 〉 2σ（I）. Structural analysis shows that 1 displays an isolated dinuclear structure. Two eight-coordinated Tb（Ⅲ） ions are bridged by four 4-cba ligands in the syn-syn bidentate coordination mode, and two other 4-cba ligands chelate these two Tb（Ⅲ） ions. The title complex molecules are connected through π-π stacking interactions to generate a one-dimensional supramolecular chain, The characteristic infrared spectra, luminescent properties and thermogravimetric analyses have also been discussed.展开更多
文摘The two complexes [Cu(C5H2N2O4)(H2O)3]·2H2O (1) and [Ni(C5H2N2O4)(H2O)4]·H2O (2) were synthesized by self assembly reactions of Cu(NO3)2·3H2O or Ni(CH3COO)2·4H2O with orotic acid (2,6 dioxo 1,2,3,6 tetrahydro 4 pyrimidinecarboxylic acid), respectively. Their crystal structures were determined by single crystal X ray diffraction analyses. Crystallographic data for complex 1: C5H8N2CuO7·2H2O, Mr=307.7, monoclinic P21/n, a=0.57710(1)nm, b=1.76863(6)nm, c=1.09955(4)nm, β=98.600(2)°, V=1.109.63(6)nm3, Z=4 , Dc=1.842g·cm-3, μ(MoKα)=2.010mm-1, F(000)=628, R=0.0436, wR=0.1015, And for complex 2: C5H10N2NiO8·H2O, Mr=302.88, orthorhombic Pbcn, a=2.0763(1)nm, b=1.69355(9)nm, c=0.73478(4)nm, V=2.5837(2)nm3, Z=8, Dc=1.557g·cm-3, μ(MoKα)=1.538 mm-1, F(000)=1248, R=0.0545, wR=0.1305. The X ray analyses revealed that the Cu? and Ni? atoms are both coordinated by carboxylic O atom and contiguous N atom of the pyrimidine ring. In complex 1 the Cu? atom has a slightly distorted square pyramid coordination environment with additional three water molecules, while in complex 2 the Ni? atom adopts a slightly distorted octahedral geometry with additional four water molecules. The three dimensional frameworks of the two complexes are formed by intermolecular hydrogen bonding interactions. CCDC: 1, 204881; 2, 204882.
基金the Natural Science Foundation of China, Fujian Province and Chinese Academy of Sciences.
文摘The title complex was prepared from self-assembly reaction of La（NO3）3(6H2O, Zn（NO3）2(6H2O, m-cyanobenzoic acid （m-CNC6H4COOH） and pyridine （Py） in refluxing ethanol and its structure was determined by single-crystal X-ray diffraction. Crystallographic data: C94H62N12La2O22Zn2, Mr = 2120.12, triclinic space group P, a = 13.2219（5）, b = 13.2713（5）, c = 14.1987（6） ?, (???69.156（1）, ( = 84.034（1）, ( = 89.400（1） (, V = 2314.9（2） ?3, Z = 1, Dc = 1.521 g/cm3, F（000） = 1060, ( (MoK（） = 14.94 cm－1, the final R = 0.043 and wR = 0.117 for 6381 unique reflections with I > 2(（I）. Crystal structure determination shows that the neighboring lanthanum（III） and zinc（II） ions are bridged by three bidentate m-cyanobenzonate ligands in the syn-syn fashion to form a pair of dinuclear [LaZn（m-CNC6H4COO）3（Py）（C2H5OH）] subunits, being linked together by two bidentate and two tridentate m-cyanobenzonate groups in the syn-syn and syn-anti modes, respectively, to construct a tetranuclear La-Zn complex [La2Zn2（m-CNC6H4COO）10（Py）2（C2H5OH）2].
基金the Natural Science Foundation of China Fujian Province and Chinese Academy of Sciences.
文摘A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.
文摘The title compound (C_ 24H_ 40Cl_6O_ 16V_3, M_r = 950.08) was synthesized from the reaction of VCl_3 and NaO_2CEt in CHCl_3 and THF. The crystal structure has been determined by X-ray single-crystal diffraction analysis. It crystallizes in monoclinic space group C2/c with a = 12.5768(4), b= 16.5601(4), c = 19.3574(7) , β = 99.879(1)°, V = 3971.3(2)3, D_c = 1.589 g/cm3, μ= 1.157 mm -1, F(000)=1932, Z=4, R = 0.055, wR = 0.1539 (I2σ(I)). This compound has an unusual coplanar V_3O core with a C_2 axis passing through O(1), V(1), O(10): one V-μ_3O is short (1.628 ), the other two are longer (2.381 ). It was characterized by IR, 1H NMR, and EPR spectra. It was unstable and the decomposition process of this compound was studied using IR spectroscopy.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020)+1 种基金and Natural Science Foundation of Fujian Province (2003I031 A0420002)
文摘The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.
基金Supported by NSFC(No.21431004,21522104 and 21620102001)“973”Program(No.2014CB932102 and 2016YFA0203400)+1 种基金the Shanghai“Eastern Scholar”Program SSTC-14YF1401300the Key Project of Basic Research of Shanghai(17JC1403100)
文摘A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra（FTIR）, circular dichroism（CD） and thermogravimetric analyses（TGA）. Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.
基金the National Natural Science Foundation of China (20671091) Natural Science of Fujian Province (A0420002 and 2005I017)
文摘A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C72H40N10O12Tb2, Mr=1554.98, triclinic Pi, a = 9.903（3）, b = 11.769（8）, c = 15.078（8）A, a = 111.42（12）, It = 96.37（19）, γ = 101-24（14）°, V= 1572（1）A3, Z= 1, Dc = 1.642 g/cm^3, F（000） = 768 μ = 2.305 mm^-1, the final R = 0.0205 and wR = 0.0543 for 5479 reflections with I 〉 2σ（I）. Structural analysis shows that 1 displays an isolated dinuclear structure. Two eight-coordinated Tb（Ⅲ） ions are bridged by four 4-cba ligands in the syn-syn bidentate coordination mode, and two other 4-cba ligands chelate these two Tb（Ⅲ） ions. The title complex molecules are connected through π-π stacking interactions to generate a one-dimensional supramolecular chain, The characteristic infrared spectra, luminescent properties and thermogravimetric analyses have also been discussed.
