Two Mo/S complexes:K6[Mo2O2S2（C2O4）2（ClPO3）2]·H2O（1）andK6[Mo2O3S（C2O4）2（ClPO3）2]·3H2O（2）containing oxalate ligand were prepared by the reaction of（NH4）2MoS4 and potassiu oxalate with adding a s...Two Mo/S complexes:K6[Mo2O2S2（C2O4）2（ClPO3）2]·H2O（1）andK6[Mo2O3S（C2O4）2（ClPO3）2]·3H2O（2）containing oxalate ligand were prepared by the reaction of（NH4）2MoS4 and potassiu oxalate with adding a small amount of H3PO4 to adjust the value of pH in system of methanol and water under an atmosphere of pure nitrogen at ambient temperature and charcterized by the means of elemental analysis,IR,UV-vis.The analysis results reveal that crystal of the complex 1 is Orthorhombic,space group pbcn,a=4.6370（2）nm,b=0.7549（2）nm,c=1.3888（4）nm,V=4.861（2）nm3,Z=8,Mr=945.49,Dc=2.58g/cm3,μ=2.625cm-1,R=0.063,wR=0.075.In addition,The their spectral properties were also discussed.展开更多
The complex-(4’-fluorobenzyl)pyridiniu 2Ni (dto) 2(dto 2- means dithiooxalate dianion)has been pre-pared by reaction of Na 2Ni (S 2 C 2 O 2 ) 2and the 1-(4’-fluorobenzyl)pyridinium chloride salt.The crystallographic...The complex-(4’-fluorobenzyl)pyridiniu 2Ni (dto) 2(dto 2- means dithiooxalate dianion)has been pre-pared by reaction of Na 2Ni (S 2 C 2 O 2 ) 2and the 1-(4’-fluorobenzyl)pyridinium chloride salt.The crystallographic data for the title complex:triclini cP1,a=8.5698(8)?,b=9.3461(9)?,c=10.5361(10)?,α=67.177(2)°,β=67.398(2)°,γ=79.611(2)°,V=717.59(12)? 3 ,Z =1.TheNi (dto) 2 2- anion with the Ni atom lying on an inversion center and exhi bits a quasi-planar structure.An extensive hydrogen bond network of C -H...O is clearly observed.The nature and size of cation seems to play an important factor in the type of intermolecu lar interactions as well as the crystal packing in this kind of complexes.展开更多
According to the principles of simultaneous equilibrium and mass equilibrium, a series of thermodynamic equilibrium equations in Ni（II）-Co（II）-C2O4^2--NH3-NH4^＋-H2O system at ambient temperature were deduced. The...According to the principles of simultaneous equilibrium and mass equilibrium, a series of thermodynamic equilibrium equations in Ni（II）-Co（II）-C2O4^2--NH3-NH4^＋-H2O system at ambient temperature were deduced. The diagrams of logarithm ion concentrations versus pH values at different solution compositions were drawn. The results show that Ni^2＋ and Co^2＋ can completely precipitate at pH less than 5.0 and the predefined Ni/Co ratios can be well kept in the precursor. The precursor morphology is granular aggregation. However, rod aggregation precursor is obtained in the pH range of 5.0-8.0, and fibre-shape precursor is got at pH value higher than 8.0. The Ni/Co ratios in the above two precursors are not reproduced as that in the feed due to the formhtion of multi-coordinated Ni（NH3）n^2＋ and Co（NH3）n^2＋ （n=1-6）. Modification of precipitation medium is favorable for the precursors to keep the predefined Ni/Co ratios of the feed in the pH range of 2.0-8.6. Meanwhile, the precursors with fibrous morphology can be obtained.展开更多
The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs...The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.展开更多
文摘Two Mo/S complexes:K6[Mo2O2S2（C2O4）2（ClPO3）2]·H2O（1）andK6[Mo2O3S（C2O4）2（ClPO3）2]·3H2O（2）containing oxalate ligand were prepared by the reaction of（NH4）2MoS4 and potassiu oxalate with adding a small amount of H3PO4 to adjust the value of pH in system of methanol and water under an atmosphere of pure nitrogen at ambient temperature and charcterized by the means of elemental analysis,IR,UV-vis.The analysis results reveal that crystal of the complex 1 is Orthorhombic,space group pbcn,a=4.6370（2）nm,b=0.7549（2）nm,c=1.3888（4）nm,V=4.861（2）nm3,Z=8,Mr=945.49,Dc=2.58g/cm3,μ=2.625cm-1,R=0.063,wR=0.075.In addition,The their spectral properties were also discussed.
文摘The complex-(4’-fluorobenzyl)pyridiniu 2Ni (dto) 2(dto 2- means dithiooxalate dianion)has been pre-pared by reaction of Na 2Ni (S 2 C 2 O 2 ) 2and the 1-(4’-fluorobenzyl)pyridinium chloride salt.The crystallographic data for the title complex:triclini cP1,a=8.5698(8)?,b=9.3461(9)?,c=10.5361(10)?,α=67.177(2)°,β=67.398(2)°,γ=79.611(2)°,V=717.59(12)? 3 ,Z =1.TheNi (dto) 2 2- anion with the Ni atom lying on an inversion center and exhi bits a quasi-planar structure.An extensive hydrogen bond network of C -H...O is clearly observed.The nature and size of cation seems to play an important factor in the type of intermolecu lar interactions as well as the crystal packing in this kind of complexes.
基金Project (20090162120080) supported by Research Fund for the Doctoral Program of Higher Education of China Project (20070410989) supported by China Postdoctoral Science Foundation+1 种基金 Project (2010FJ3012) supported by the Program of Science and Technology of Hunan Province, China Project (09JJ4028) supported by Natural Science Foundation of Hunan Province, China
文摘According to the principles of simultaneous equilibrium and mass equilibrium, a series of thermodynamic equilibrium equations in Ni（II）-Co（II）-C2O4^2--NH3-NH4^＋-H2O system at ambient temperature were deduced. The diagrams of logarithm ion concentrations versus pH values at different solution compositions were drawn. The results show that Ni^2＋ and Co^2＋ can completely precipitate at pH less than 5.0 and the predefined Ni/Co ratios can be well kept in the precursor. The precursor morphology is granular aggregation. However, rod aggregation precursor is obtained in the pH range of 5.0-8.0, and fibre-shape precursor is got at pH value higher than 8.0. The Ni/Co ratios in the above two precursors are not reproduced as that in the feed due to the formhtion of multi-coordinated Ni（NH3）n^2＋ and Co（NH3）n^2＋ （n=1-6）. Modification of precipitation medium is favorable for the precursors to keep the predefined Ni/Co ratios of the feed in the pH range of 2.0-8.6. Meanwhile, the precursors with fibrous morphology can be obtained.
文摘The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.
