Divanadium（Ⅴ） complex [VO（aptch）（μ-OCH3）]2（1） and two monovanadium（Ⅴ） complexes [VO（apfah））（OEt）]（2a and 2b,H2aptch = 2-hydroxyacetophenone thiophene-2-car-boxylic hydrazone,H2apfah = 2-hydroxyaceto...Divanadium（Ⅴ） complex [VO（aptch）（μ-OCH3）]2（1） and two monovanadium（Ⅴ） complexes [VO（apfah））（OEt）]（2a and 2b,H2aptch = 2-hydroxyacetophenone thiophene-2-car-boxylic hydrazone,H2apfah = 2-hydroxyacetophenone 2-furoic acid hydrazone） have been synthesized and characterized.Single-crystal X-ray diffraction studies reveal that 1 is a cen-trosymmetric dimer bridged by two methoxido O-atoms.Complex 1 crystallizes in the monoclinic crystal system,space groups P21/c with a = 7.4825（4）,b = 17.0928（11）,c = 11.6961（7） ,β = 98.172（4）o,Z = 2,F（000） = 728,μ = 0.829 mm-1,the final R = 0.0457 and wR = 0.1137 for 2654 observed reflections with I 〉 2（I）.The vanadium（V） is coordinated to the tridentate ligand,ethanol molecule to form a distorted square-pyramidal geometry,complexes 2a and 2b.Although 2a and 2b have the same asymmetric unit,they belong to different space groups.Complex 2a crystallizes in the monoclinic crystal system,space groups P21/n with a = 10.2293（2）,b = 15.6660（3）,c = 10.6298（2） ,β = 116.259（1）o,Z = 4,μ = 0.676 mm-1;complex 2b crystallizes in the triclinic crystal system,space groups P with a = 8.2808（4）,b = 9.4704（5）,c = 10.0819（5） ,α = 86.133（3）,= 81.956（3）,γ = 80.248（3）o,Z = 2 and μ = 0.670 mm-1.The hydrogen bonds are found to exist in 2b only.The crystal structure is stabilized by intermolecular hydrogen bonds of C-H···O.展开更多
Complex VO(C\-\{12\}H\-\{12\}N\-2O\-2)(C\-\{13\}H\-\{10\}NO\-2)(C\-\{12\}H\-\{12\}N\-2O\+\{\{\}\+\{2-\}\}\-2=acetylacetone benzoylhydrozanate,C\-\{13\}H\-\{10\}NO\+_\-2=\%N\%\|phenylbenzohydroxamate) was synthesized a...Complex VO(C\-\{12\}H\-\{12\}N\-2O\-2)(C\-\{13\}H\-\{10\}NO\-2)(C\-\{12\}H\-\{12\}N\-2O\+\{\{\}\+\{2-\}\}\-2=acetylacetone benzoylhydrozanate,C\-\{13\}H\-\{10\}NO\+_\-2=\%N\%\|phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis,IR and UV spectroscopies,cyclic voltammetry and single crystal X\|ray diffraction. The complex crystallized in the monoclinic system with space group \%P\%2\-1/\%n\% and the crystal cell parameters \%a\%=1\^3003(1) nm,\%b\%=0\^88836(6) nm,\%c\%=2\^0196(2) nm,\%β\%=95\^065(8)°,\%V\%=2\^3238(3) nm\+3,\%M\%\-r=495\^40 and \%Z\%=4. The two oxygen and one nitrogen atoms of the tridentate hydrazone ligand coordinate to the vanadium atom,forming an equatorial plane. And the coordinated vanadium atom exhibits a distorted octahedral geometry. The atom in the transposition to the oxo O atom is the carbonyl oxygen atom of the hydroxamate ligand in the complex. The half\|wave redox potential of the title complex in the three different solvents positively shifts in the order of CH\-2Cl\-2<CH\-3CN<DMF.展开更多
基金supported by the Scientific Research Common Program of Beijing Municipal Commission of Education,PRC (KM200910028011)
文摘Divanadium（Ⅴ） complex [VO（aptch）（μ-OCH3）]2（1） and two monovanadium（Ⅴ） complexes [VO（apfah））（OEt）]（2a and 2b,H2aptch = 2-hydroxyacetophenone thiophene-2-car-boxylic hydrazone,H2apfah = 2-hydroxyacetophenone 2-furoic acid hydrazone） have been synthesized and characterized.Single-crystal X-ray diffraction studies reveal that 1 is a cen-trosymmetric dimer bridged by two methoxido O-atoms.Complex 1 crystallizes in the monoclinic crystal system,space groups P21/c with a = 7.4825（4）,b = 17.0928（11）,c = 11.6961（7） ,β = 98.172（4）o,Z = 2,F（000） = 728,μ = 0.829 mm-1,the final R = 0.0457 and wR = 0.1137 for 2654 observed reflections with I 〉 2（I）.The vanadium（V） is coordinated to the tridentate ligand,ethanol molecule to form a distorted square-pyramidal geometry,complexes 2a and 2b.Although 2a and 2b have the same asymmetric unit,they belong to different space groups.Complex 2a crystallizes in the monoclinic crystal system,space groups P21/n with a = 10.2293（2）,b = 15.6660（3）,c = 10.6298（2） ,β = 116.259（1）o,Z = 4,μ = 0.676 mm-1;complex 2b crystallizes in the triclinic crystal system,space groups P with a = 8.2808（4）,b = 9.4704（5）,c = 10.0819（5） ,α = 86.133（3）,= 81.956（3）,γ = 80.248（3）o,Z = 2 and μ = 0.670 mm-1.The hydrogen bonds are found to exist in 2b only.The crystal structure is stabilized by intermolecular hydrogen bonds of C-H···O.
文摘Complex VO(C\-\{12\}H\-\{12\}N\-2O\-2)(C\-\{13\}H\-\{10\}NO\-2)(C\-\{12\}H\-\{12\}N\-2O\+\{\{\}\+\{2-\}\}\-2=acetylacetone benzoylhydrozanate,C\-\{13\}H\-\{10\}NO\+_\-2=\%N\%\|phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis,IR and UV spectroscopies,cyclic voltammetry and single crystal X\|ray diffraction. The complex crystallized in the monoclinic system with space group \%P\%2\-1/\%n\% and the crystal cell parameters \%a\%=1\^3003(1) nm,\%b\%=0\^88836(6) nm,\%c\%=2\^0196(2) nm,\%β\%=95\^065(8)°,\%V\%=2\^3238(3) nm\+3,\%M\%\-r=495\^40 and \%Z\%=4. The two oxygen and one nitrogen atoms of the tridentate hydrazone ligand coordinate to the vanadium atom,forming an equatorial plane. And the coordinated vanadium atom exhibits a distorted octahedral geometry. The atom in the transposition to the oxo O atom is the carbonyl oxygen atom of the hydroxamate ligand in the complex. The half\|wave redox potential of the title complex in the three different solvents positively shifts in the order of CH\-2Cl\-2<CH\-3CN<DMF.
