[Cd(NTO)4Cd(H2O)6] ?4H2O was synthesized by mixing the aqueous solution of 3-nitro-1, 2,4-triazol-5-one (NTO) and cadmium carbonate. The single crystal structure was determined by a four-circle X-ray diffractometer. T...[Cd(NTO)4Cd(H2O)6] ?4H2O was synthesized by mixing the aqueous solution of 3-nitro-1, 2,4-triazol-5-one (NTO) and cadmium carbonate. The single crystal structure was determined by a four-circle X-ray diffractometer. The crystal is monoclinic, space group C2/c with crystal parameters of a = 2.1229(3) nm, b = 0.6261(8) nm, = 2.1165(3) nm, β= 90.602 (3)°, V= 2.977(6) nm3, Z = 4, Dc = 2.055 g ? cm-3, μ = 15.45 cm-1 and F(000) = 1824. 2523 observable independent reflections with F04σ(F0) were used for the determination and refinement of the crystal structure. Lorentz-polarization and absorption correction were applied. The final R is 0.0282 and wR = 0.0792. The analytical results show that the Cd+2 has two kinds of coordinate bonds in one crystal. One Cd+2 coordinates with 4 NTO anions and another coordinates with 6 water molecules to form a binucleate complex with a structure of tetrahedron and tetragonal bipyramid, respectively. By using SCF-PM3-MO method, the electron structure of cadmium complex of NTO has been calculated. The analysis of the calculated results shows that when [Cd(NTO)4Cd(H2O)6] ? 4H2O is heated, the crystallization waters will be dissociated first and the ligand waters second and NO2 group has priority of leaving when NTO? is decomposed. Analysis of the energy level and composition of localized molecular orbitals indicates that both the two Cd2+ bond to the coordinating atom with 5s展开更多
基金supported by the National Natural Science Foundation of China(Grant No.29971025)the Backbone Teacher of Chinese University Sustentation Fund of the Ministry of Education,China.
文摘[Cd(NTO)4Cd(H2O)6] ?4H2O was synthesized by mixing the aqueous solution of 3-nitro-1, 2,4-triazol-5-one (NTO) and cadmium carbonate. The single crystal structure was determined by a four-circle X-ray diffractometer. The crystal is monoclinic, space group C2/c with crystal parameters of a = 2.1229(3) nm, b = 0.6261(8) nm, = 2.1165(3) nm, β= 90.602 (3)°, V= 2.977(6) nm3, Z = 4, Dc = 2.055 g ? cm-3, μ = 15.45 cm-1 and F(000) = 1824. 2523 observable independent reflections with F04σ(F0) were used for the determination and refinement of the crystal structure. Lorentz-polarization and absorption correction were applied. The final R is 0.0282 and wR = 0.0792. The analytical results show that the Cd+2 has two kinds of coordinate bonds in one crystal. One Cd+2 coordinates with 4 NTO anions and another coordinates with 6 water molecules to form a binucleate complex with a structure of tetrahedron and tetragonal bipyramid, respectively. By using SCF-PM3-MO method, the electron structure of cadmium complex of NTO has been calculated. The analysis of the calculated results shows that when [Cd(NTO)4Cd(H2O)6] ? 4H2O is heated, the crystallization waters will be dissociated first and the ligand waters second and NO2 group has priority of leaving when NTO? is decomposed. Analysis of the energy level and composition of localized molecular orbitals indicates that both the two Cd2+ bond to the coordinating atom with 5s
