The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu<sup>+</sup>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Co<sup>3+</sup> chloride and/or iodi...The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu<sup>+</sup>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Co<sup>3+</sup> chloride and/or iodide afford new metal complexes. The isolated complexes were synthesized by two different techniques (chemical and tribochemical methods). Two complexes were synthesized by the direct chemical reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) with MCl<sub>2</sub>·XH<sub>2</sub>O (M = Co<sup>2+</sup> and Cu<sup>2+</sup>;X = 6 in case of Co<sup>2+</sup> and X = 2 in case of Cu<sup>2+</sup>) in absolute EtOH. The general formulae of the two complexes derived by the chemical method are [Cu(L)<sub>2</sub>(EtOH)<sub>2</sub>]Cl<sub>2</sub> and [Co(L)<sub>2</sub>Cl<sub>2</sub>]Cl. These complexes were used to synthesize another two complexes using tribochemical reaction by grinding the previous chloride complexes with excess KI in agate mortar in the solid state. The isolated complexes have the general formulae, [Cu(L)I·H<sub>2</sub>O]·1/2H<sub>2</sub>O and [Co(L)I<sub>3</sub>(Et- OH)]·3EtOH. The results indicate the substitution of the chloride by iodide ions during grinding and extraction of the complexes by solvents. The IR spectra of the complexes suggest that L acts in a bidentate manner towards the metal ions. Moreover, the results of electronic spectra and magnetic measurements for the chloride complexes suggest distorted-octahedral structure for Cu<sup>2+</sup> and low-spin octahedral structures around the Co<sup>II</sup> and Cu<sup>2+</sup> ions, respectively. On the other hand the data suggest that the iodide complexes have square-planer and low-spin for the Cu<sup>+</sup> and Co<sup>3+</sup> ions, respectively. The results of mass spectra confirm the formulae proposed for the isolated complexes. The mechanisms of reduction of Cu<sup>II</sup> and oxidation of Co<sup>II</sup> for the metal complexes were elucidated.展开更多
Herein,we demonstrated that poly（ethylene oxide）（PEO）,urea and thiourea can crystallize into novel ternary complex with the molar ratio of vip polymer and host small molecule as 3：2,and proved that the ternary ...Herein,we demonstrated that poly（ethylene oxide）（PEO）,urea and thiourea can crystallize into novel ternary complex with the molar ratio of vip polymer and host small molecule as 3：2,and proved that the ternary complex behaves isomorphism phenomenon by varying the ratio between urea and thiourea for the first time.This observation gives a boost to prepare co-crystals of different small molecules that cannot be obtained by direct mixing without the aid of polymer chains.展开更多
The title compound Fe(CH4N2S)2Cl22(C11H6N2O) (Mr = 643.35) has been prepared and its crystal structure was determined by X-ray diffraction method with the following data: triclinic, space group P1, a = 7.3742(10), b =...The title compound Fe(CH4N2S)2Cl22(C11H6N2O) (Mr = 643.35) has been prepared and its crystal structure was determined by X-ray diffraction method with the following data: triclinic, space group P1, a = 7.3742(10), b = 13.0427(12), c = 15.215(2) , a = 88.969(12), b = 78.004(12), g = 79.689(11)o, V = 1408.1(3) 3, Z = 2, Dx = 1.517 g/cm3, m = 0.912 mm-1 and F(000) = 656. The final R = 0.030 and wR = 0.078 for 4070 observed reflections (I > 2s(I)), and R = 0.064 and wR = 0.091 for 5516 independent ones. The crystal consists of tetrahedral Fe(II) complex and hydrogen bonded 4,5-diazafluoren-9-one (dafone). The carbonyl bridge in dafone distorts the bipyridine moiety and results in the longer N…N separation of 3.071(3) and 3.061(3) ? There exists an extensive intermolecular hydrogen bond network in the crystal, and p-p stacking is observed between the neighboring dafone rings.展开更多
A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385...A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385（7）, c = 22.0008（18） A, β = 108.077（2）°, V = 3104.3（5） A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ（MoKa） = 0.920 mm^-1, F（000） = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections （I 〉 2σ（I））. X-ray diffraction shows the existence of weak complementary intramolecular N-H...O （DA） hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu（Ⅱ） ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.展开更多
Several mixed ligand Cu(II), Zn(II) complexes using (benzylidenethiourea) (obtained by the condensation of benzaldehyde and thiourea) as the primary ligand and (acetamide or thioacetamide) as an additional ligand were...Several mixed ligand Cu(II), Zn(II) complexes using (benzylidenethiourea) (obtained by the condensation of benzaldehyde and thiourea) as the primary ligand and (acetamide or thioacetamide) as an additional ligand were synthesized and characterized analytically and spectroscopically, magnetic susceptibility and molar conductance measurements ,as well as by UV-Vis. and IR spectroscopy. The interaction of the complexes with calf thymus (CT)DNA was studied using absorption spectra, while the concentration of DNA in gel electrophoresis remained constant at 10 μl. They exhibit absorption hypochromicity increased during the binding of the complexes to calf thymus DNA. The complexes show enhanced antimicrobial activities complexes with the free ligand. A theoretical treatment of the formation of complexes in the gas phase was studied, this was done using the HYPERCHEM-6 program for the Molecular mechanics and Semi-empirical calculations.展开更多
文摘The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu<sup>+</sup>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Co<sup>3+</sup> chloride and/or iodide afford new metal complexes. The isolated complexes were synthesized by two different techniques (chemical and tribochemical methods). Two complexes were synthesized by the direct chemical reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) with MCl<sub>2</sub>·XH<sub>2</sub>O (M = Co<sup>2+</sup> and Cu<sup>2+</sup>;X = 6 in case of Co<sup>2+</sup> and X = 2 in case of Cu<sup>2+</sup>) in absolute EtOH. The general formulae of the two complexes derived by the chemical method are [Cu(L)<sub>2</sub>(EtOH)<sub>2</sub>]Cl<sub>2</sub> and [Co(L)<sub>2</sub>Cl<sub>2</sub>]Cl. These complexes were used to synthesize another two complexes using tribochemical reaction by grinding the previous chloride complexes with excess KI in agate mortar in the solid state. The isolated complexes have the general formulae, [Cu(L)I·H<sub>2</sub>O]·1/2H<sub>2</sub>O and [Co(L)I<sub>3</sub>(Et- OH)]·3EtOH. The results indicate the substitution of the chloride by iodide ions during grinding and extraction of the complexes by solvents. The IR spectra of the complexes suggest that L acts in a bidentate manner towards the metal ions. Moreover, the results of electronic spectra and magnetic measurements for the chloride complexes suggest distorted-octahedral structure for Cu<sup>2+</sup> and low-spin octahedral structures around the Co<sup>II</sup> and Cu<sup>2+</sup> ions, respectively. On the other hand the data suggest that the iodide complexes have square-planer and low-spin for the Cu<sup>+</sup> and Co<sup>3+</sup> ions, respectively. The results of mass spectra confirm the formulae proposed for the isolated complexes. The mechanisms of reduction of Cu<sup>II</sup> and oxidation of Co<sup>II</sup> for the metal complexes were elucidated.
基金Financial support from the National Natural Science Foundation of China(Nos.21304108 and 21674128)
文摘Herein,we demonstrated that poly（ethylene oxide）（PEO）,urea and thiourea can crystallize into novel ternary complex with the molar ratio of vip polymer and host small molecule as 3：2,and proved that the ternary complex behaves isomorphism phenomenon by varying the ratio between urea and thiourea for the first time.This observation gives a boost to prepare co-crystals of different small molecules that cannot be obtained by direct mixing without the aid of polymer chains.
基金This work was supported by the National Natural Science Foundation of China (29973036)
文摘The title compound Fe(CH4N2S)2Cl22(C11H6N2O) (Mr = 643.35) has been prepared and its crystal structure was determined by X-ray diffraction method with the following data: triclinic, space group P1, a = 7.3742(10), b = 13.0427(12), c = 15.215(2) , a = 88.969(12), b = 78.004(12), g = 79.689(11)o, V = 1408.1(3) 3, Z = 2, Dx = 1.517 g/cm3, m = 0.912 mm-1 and F(000) = 656. The final R = 0.030 and wR = 0.078 for 4070 observed reflections (I > 2s(I)), and R = 0.064 and wR = 0.091 for 5516 independent ones. The crystal consists of tetrahedral Fe(II) complex and hydrogen bonded 4,5-diazafluoren-9-one (dafone). The carbonyl bridge in dafone distorts the bipyridine moiety and results in the longer N…N separation of 3.071(3) and 3.061(3) ? There exists an extensive intermolecular hydrogen bond network in the crystal, and p-p stacking is observed between the neighboring dafone rings.
基金the National Natural Science Foundation of China (No.20571060)Education Committee of Shaanxi Province (05JK294)Xi'an Scientific and Technical Plan Project (No. YF07106)
文摘A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385（7）, c = 22.0008（18） A, β = 108.077（2）°, V = 3104.3（5） A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ（MoKa） = 0.920 mm^-1, F（000） = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections （I 〉 2σ（I））. X-ray diffraction shows the existence of weak complementary intramolecular N-H...O （DA） hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu（Ⅱ） ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.
文摘Several mixed ligand Cu(II), Zn(II) complexes using (benzylidenethiourea) (obtained by the condensation of benzaldehyde and thiourea) as the primary ligand and (acetamide or thioacetamide) as an additional ligand were synthesized and characterized analytically and spectroscopically, magnetic susceptibility and molar conductance measurements ,as well as by UV-Vis. and IR spectroscopy. The interaction of the complexes with calf thymus (CT)DNA was studied using absorption spectra, while the concentration of DNA in gel electrophoresis remained constant at 10 μl. They exhibit absorption hypochromicity increased during the binding of the complexes to calf thymus DNA. The complexes show enhanced antimicrobial activities complexes with the free ligand. A theoretical treatment of the formation of complexes in the gas phase was studied, this was done using the HYPERCHEM-6 program for the Molecular mechanics and Semi-empirical calculations.
