Syntheses, Structures, and Some Properties of Three Vanadium Selenites  

作　　者：赵宁 张甲敏 娄天军 李浩宏 

机构地区：[1]School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology [2]School of Chemistry and Chemical Engineering,Fuzhou University

出　　处：《Chinese Journal of Structural Chemistry》2009年第4期445-452,共8页结构化学（英文）

基　　金：Supported by the Natural Science Foundation of Henan Institute of Science and Technology (No. 06038)

摘　　要：Three novel vanadium selenites with the formulae [（VO2）（1,10-phenanthtoline）（SeO3H）]2 1, [（VO2）（2,2′-bipyridine）]2（SeO3） 2 and [（VO）（H2O）（SeO3）2]2（HaEDD） 3 （EDD = N1,N1′-（ethane-1,2-diyl）diethane-1,2-diamine） were hydrothermally synthesized, and characterized with elemental analysis, FT-IR spectrum, Raman spectrum, TG-DTA analysis, EPR spectra, and single-crystal X-ray diffraction analysis. Compound I belongs to the triclinic system, space group P1^- with a = 7.7527（5）, b = 9.5345（10）, c = 9.8192（8） A^°, α = 92.712（3）, β = 105.540（3）, γ = 108.154（4）°, V = 657.66（1） A^°^3, Mr = 782.22, Z = 1, F（000） = 384,μ（MoKa） = 3.544 mm^-1, R = 0.0432 and wR = 0.1142; Compound 2 is of orthorhombic system, space group F212121 with a = 7.6574（15）, b = 14.916（3）, c = 19.085（4） A, V = 2179.8（8） Aa, Mr = 605.21, Z = 4, F（000） = 1200, μ（MoKa） = 2.579 mm^-1, R = 0.0338 and wR = 0.0658; Compound 3 belongs to the triclinic system, space group P1^- with a = 9.247（2）, b = 9.659（2）, c = 7.2651（19） A^°, α = 98.171（7）, β = 103.709（5）, γ = 114.712（13）°, V = 550.9（2） A^°^3, Mr = 828.03, Z = 1, F（000） = 400, μ（MoKa） = 7.537 mm^-1, R = 0.0641 and wR = 0.2118. Compound 1 is constructed from alternating corner-shared [VO4N2] octahedra and SeO3H units, forming a dimeric vanadium unit. These assemblies are further linked into an infinite chain via hydrogen bonds along the a axis. In the structure of 2, two distinct V centers form centrosymmetric [V2O6N4] clusters through edge-sharing, and the SeO3 unit serves as a capping unit to fix the oxovanadate cluster. In the structure of 3, each [VO6] octahedron shares four oxygen atoms with adjacent Se atoms, while every SeO3 unit shares two oxygen atoms with neighboring V atoms. This connectivity of alternating VO6 and SeO3 units results in a joint-like chain. Based on the TGA analysis, these three compounds are thermally stable under 200℃ .Three novel vanadium selenites with the formulae [（VO2）（1,10-phenanthtoline）（SeO3H）]2 1, [（VO2）（2,2′-bipyridine）]2（SeO3） 2 and [（VO）（H2O）（SeO3）2]2（HaEDD） 3 （EDD = N1,N1′-（ethane-1,2-diyl）diethane-1,2-diamine） were hydrothermally synthesized, and characterized with elemental analysis, FT-IR spectrum, Raman spectrum, TG-DTA analysis, EPR spectra, and single-crystal X-ray diffraction analysis. Compound I belongs to the triclinic system, space group P1^- with a = 7.7527（5）, b = 9.5345（10）, c = 9.8192（8） A^°, α = 92.712（3）, β = 105.540（3）, γ = 108.154（4）°, V = 657.66（1） A^°^3, Mr = 782.22, Z = 1, F（000） = 384,μ（MoKa） = 3.544 mm^-1, R = 0.0432 and wR = 0.1142; Compound 2 is of orthorhombic system, space group F212121 with a = 7.6574（15）, b = 14.916（3）, c = 19.085（4） A, V = 2179.8（8） Aa, Mr = 605.21, Z = 4, F（000） = 1200, μ（MoKa） = 2.579 mm^-1, R = 0.0338 and wR = 0.0658; Compound 3 belongs to the triclinic system, space group P1^- with a = 9.247（2）, b = 9.659（2）, c = 7.2651（19） A^°, α = 98.171（7）, β = 103.709（5）, γ = 114.712（13）°, V = 550.9（2） A^°^3, Mr = 828.03, Z = 1, F（000） = 400, μ（MoKa） = 7.537 mm^-1, R = 0.0641 and wR = 0.2118. Compound 1 is constructed from alternating corner-shared [VO4N2] octahedra and SeO3H units, forming a dimeric vanadium unit. These assemblies are further linked into an infinite chain via hydrogen bonds along the a axis. In the structure of 2, two distinct V centers form centrosymmetric [V2O6N4] clusters through edge-sharing, and the SeO3 unit serves as a capping unit to fix the oxovanadate cluster. In the structure of 3, each [VO6] octahedron shares four oxygen atoms with adjacent Se atoms, while every SeO3 unit shares two oxygen atoms with neighboring V atoms. This connectivity of alternating VO6 and SeO3 units results in a joint-like chain. Based on the TGA analysis, these three compounds are thermally stable under 200℃ .

关 键 词：vanadium selenite crystal structure complex hydrothermal reaction inorganic-organic hybrid material 

分 类 号：O611.3[理学—无机化学]