利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 48...利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 4805.1(17) 3, Z = 4, Dc = 2.051 g/cm3, m = 1.431 mm-1, F(000) = 3000, I >2s(I) 的可观察衍射点4426个, 最终结构偏差因子R = 0.0464, wR = 0.0801, S = 0.731。在[P2Mo5O23]6-杂多阴离子中5个MoO6八面体通过共边和共角相连, 形成1个近似的五角平面骨架, 2个PO4四面体加在五角平面的两侧。热性质研究表明杂多阴离子骨架在547.4 ℃左右分解。展开更多
The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10...The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10.8666(7), c=15.814(1)? α=71.482(3), β=88.528(2), γ=78.448(2)°, V=1589.4(2)3, Dc=2.510g/cm3, Z=2,μ=2.138mm-1,λ(MoKα) = 0.71073 ? F(000)=1180. The final R and wR were 0.0396 and 0.1052 for 6626 observed reflections with I ≥2σ(I), respectively. The result of the structure analysis indicates that the [Mo5O15(PO4) (HPO4)]5- anion in the title compound consists of five edge-sharing or corner-sharing MoO6 octahedra and two corner-sharing PO4 tetrahedra. Each MoO6 octahedron adopts distorted octahedral geometry.展开更多
A novel flower-like hydrated magnesium carbonate hydroxide, Mg5 （CO3 ）4 （OH）2·4H2O, with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use o...A novel flower-like hydrated magnesium carbonate hydroxide, Mg5 （CO3 ）4 （OH）2·4H2O, with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use of template or organic surfactant. Reaction time has an important effect on the final morphology of the product. The micro-structure and morphology of Mg5 （CO3）4 （OH）2·4H2O were characterized by means of X-ray diffractometry （XRD）, fieldemission scanning electron microscopy（FE-SEM）. Brunauer-Emmett-Teller（BET） surface areas of the samples were also measured. The probable formation mechanism of flower-like micro-structure was discussed. It was found that Mg5 （CO3）4（ OH）2·4H2O with flower-like micro-structure was a novel and efficient catalyst for the synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol.展开更多
The new oxovanadium(V)complex,[PyH][VO2(L)]1(salicyladehyde 5-bromo salicyloylhydrazone is abbreviated as H2L;Hpy is protonated pyridine)was obtained from a refluxed solution of VOSO4 and H2L in acetonitrile-methanol-...The new oxovanadium(V)complex,[PyH][VO2(L)]1(salicyladehyde 5-bromo salicyloylhydrazone is abbreviated as H2L;Hpy is protonated pyridine)was obtained from a refluxed solution of VOSO4 and H2L in acetonitrile-methanol-pyridine.Similarly,another new complex,[VO(L)(OCH3)]2 was synthesized by refluxing VOSO4 and H2L in methanol-pyridine.Crystal data for 1:C19H15N3O5BrV,Mr=496.2,monoclinic,P21/n,a=7.1885(3),b=9.2718(3),c=28.803(1)A,β=96.185(1)°,Z=4and V=1908.6(1)A^3;for 2:C15H12N2O5BrV,Mr=431.1,monoclinic ,P21/n,a=12.202(2),b=8.045(2),c=16.604(3)A,β=101.29(3)°,Z=4 and V=1598.4(2)A^3.The structures of 1 and 2 have been determined by X-ray analyses and reveal that the coordination environments of V atoms in both complexes are of square-based pyramid.Three of the four based donor atoms are from the tridentate“ONO”donor ligand while the fourth is one terminal oxygen atom with the V(1)-O(3)distance 1.646(4)Afor 1 and one-OCH3 group with the V(1)-O(3) distance 1.753(3)Afor 2.The V(1)-O(4) terminals occupy the axial sites in both cases.The complexes are also characterized by IR and ^1HNMR spectroscopies.展开更多
The title compound (C14H12N2O2, Mr = 240.26) crystallizes in the monoclinic system, space group P21/a with a = 7.394(1), b = 21.334(3), c = 7.423(1) ? b = 89.82(1)? V = 1170.8(3) ?, Z = 4, Dc = 1.363 g/cm3, m(MoKa) = ...The title compound (C14H12N2O2, Mr = 240.26) crystallizes in the monoclinic system, space group P21/a with a = 7.394(1), b = 21.334(3), c = 7.423(1) ? b = 89.82(1)? V = 1170.8(3) ?, Z = 4, Dc = 1.363 g/cm3, m(MoKa) = 0.93 cm-1 and F(000) = 504.00. The final R and wR are 0.0440 and 0.1370 for 2153 observed reflections (I > 2s(I)), respectively. The dihedral angle between the two phenyl rings is 52.9 and that between the NO2 group and its attached ring is 3.0. In the crystal, molecules are stacked along [100] through p…p interactions. The CH…O hydrogen bond (3.403 ? 120.4? laterally connects the stacks along [010] to form networks (001) which are further anti- parallelly connected by CH…O (3.382 ? 142.9) and p…p interactions extending along [001]. Also presented here is a brief study on the CH…O hydrogen bonds in nitro-substituted benzyl-ideneanilines which can be classified into five types, namely, )5(12R, )4(21R, )8(22R, )6(12R and )7(22R, with the first three occurring more often.展开更多
Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of ...Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.展开更多
(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvat...(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvated monomer with lanthanum(Ⅲ)in a trigonal bipyramidal coordination geometry if the cyclopentadienyl ring is regarded as occupying a single polyhedral vertex.展开更多
The new copper(II) complex Cu(C13H9N3O2Br)2H2O (N-(2-hydroxy-5-bromo- benzoyl)-N-(picolinylidene)hydrazine is abbreviated as HL ) was obtained from the refluxing solution of Cu(CH3COO)2H2O and HL in the ethanol-N, N-d...The new copper(II) complex Cu(C13H9N3O2Br)2H2O (N-(2-hydroxy-5-bromo- benzoyl)-N-(picolinylidene)hydrazine is abbreviated as HL ) was obtained from the refluxing solution of Cu(CH3COO)2H2O and HL in the ethanol-N, N-dimethylformamide mix solvent. Crystal data: triclinic, space group P , a = 10.8620(3), b = 11.7453 (3), c = 12.4417(2) ? ?= 62.255(0), ?= 79.097(2), ?= 86.764(2)? V = 1378.52(6) ?, Z = 2, Mr = 719.835, Dc = 1.734 g/cm3, F(000) = 714, (MoK) = 3.739 mm-1, T = 293(2) K, final R = 0.0594 and wR = 0.1416 for 2943 observed reflections with I > 2.0(I). The structure of Cu(C13H9N3O2Br)2H2O has been determined by X-ray analysis and revealed that two L-1 ligands coordinate to the copper(Ⅱ) ion through two oxygen and two nitrogen atoms from the hydrazine groups and two pyridine nitrogen atoms to form an elongated and distorted square-bipyramidal environment for Cu(Ⅱ). The complex is also characterized by 1H NMR展开更多
基金The paper is financially supported by NSF of Fujian Province (JA00137) by FPNSFC(E0110013)
文摘The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10.8666(7), c=15.814(1)? α=71.482(3), β=88.528(2), γ=78.448(2)°, V=1589.4(2)3, Dc=2.510g/cm3, Z=2,μ=2.138mm-1,λ(MoKα) = 0.71073 ? F(000)=1180. The final R and wR were 0.0396 and 0.1052 for 6626 observed reflections with I ≥2σ(I), respectively. The result of the structure analysis indicates that the [Mo5O15(PO4) (HPO4)]5- anion in the title compound consists of five edge-sharing or corner-sharing MoO6 octahedra and two corner-sharing PO4 tetrahedra. Each MoO6 octahedron adopts distorted octahedral geometry.
基金Supported by the National Natural Science Foundation of China(Nos.20671011,20331010,90406002and90406024)the 111 Project(No.B07012)the Key Laboratory of Structural Chemistry Foundation(No.060017).
文摘A novel flower-like hydrated magnesium carbonate hydroxide, Mg5 （CO3 ）4 （OH）2·4H2O, with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use of template or organic surfactant. Reaction time has an important effect on the final morphology of the product. The micro-structure and morphology of Mg5 （CO3）4 （OH）2·4H2O were characterized by means of X-ray diffractometry （XRD）, fieldemission scanning electron microscopy（FE-SEM）. Brunauer-Emmett-Teller（BET） surface areas of the samples were also measured. The probable formation mechanism of flower-like micro-structure was discussed. It was found that Mg5 （CO3）4（ OH）2·4H2O with flower-like micro-structure was a novel and efficient catalyst for the synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol.
基金The work was supported by the Chinese Academy of Sciences, the National Natural Science Foundation of China(20073048)the NSF of Fujian province for financial support
文摘The new oxovanadium(V)complex,[PyH][VO2(L)]1(salicyladehyde 5-bromo salicyloylhydrazone is abbreviated as H2L;Hpy is protonated pyridine)was obtained from a refluxed solution of VOSO4 and H2L in acetonitrile-methanol-pyridine.Similarly,another new complex,[VO(L)(OCH3)]2 was synthesized by refluxing VOSO4 and H2L in methanol-pyridine.Crystal data for 1:C19H15N3O5BrV,Mr=496.2,monoclinic,P21/n,a=7.1885(3),b=9.2718(3),c=28.803(1)A,β=96.185(1)°,Z=4and V=1908.6(1)A^3;for 2:C15H12N2O5BrV,Mr=431.1,monoclinic ,P21/n,a=12.202(2),b=8.045(2),c=16.604(3)A,β=101.29(3)°,Z=4 and V=1598.4(2)A^3.The structures of 1 and 2 have been determined by X-ray analyses and reveal that the coordination environments of V atoms in both complexes are of square-based pyramid.Three of the four based donor atoms are from the tridentate“ONO”donor ligand while the fourth is one terminal oxygen atom with the V(1)-O(3)distance 1.646(4)Afor 1 and one-OCH3 group with the V(1)-O(3) distance 1.753(3)Afor 2.The V(1)-O(4) terminals occupy the axial sites in both cases.The complexes are also characterized by IR and ^1HNMR spectroscopies.
文摘The title compound (C14H12N2O2, Mr = 240.26) crystallizes in the monoclinic system, space group P21/a with a = 7.394(1), b = 21.334(3), c = 7.423(1) ? b = 89.82(1)? V = 1170.8(3) ?, Z = 4, Dc = 1.363 g/cm3, m(MoKa) = 0.93 cm-1 and F(000) = 504.00. The final R and wR are 0.0440 and 0.1370 for 2153 observed reflections (I > 2s(I)), respectively. The dihedral angle between the two phenyl rings is 52.9 and that between the NO2 group and its attached ring is 3.0. In the crystal, molecules are stacked along [100] through p…p interactions. The CH…O hydrogen bond (3.403 ? 120.4? laterally connects the stacks along [010] to form networks (001) which are further anti- parallelly connected by CH…O (3.382 ? 142.9) and p…p interactions extending along [001]. Also presented here is a brief study on the CH…O hydrogen bonds in nitro-substituted benzyl-ideneanilines which can be classified into five types, namely, )5(12R, )4(21R, )8(22R, )6(12R and )7(22R, with the first three occurring more often.
基金PhD Special Research Foundation of Chinese Education Department (No. 20040422010)the Scientific Research Foundation of Yangzhou University
文摘Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.
文摘(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvated monomer with lanthanum(Ⅲ)in a trigonal bipyramidal coordination geometry if the cyclopentadienyl ring is regarded as occupying a single polyhedral vertex.
基金Acknowledgments: The authors thank the Chinese Academy of Sciences the National Science Foundation of China (20073048)the NSF of Fujian for financial support
文摘The new copper(II) complex Cu(C13H9N3O2Br)2H2O (N-(2-hydroxy-5-bromo- benzoyl)-N-(picolinylidene)hydrazine is abbreviated as HL ) was obtained from the refluxing solution of Cu(CH3COO)2H2O and HL in the ethanol-N, N-dimethylformamide mix solvent. Crystal data: triclinic, space group P , a = 10.8620(3), b = 11.7453 (3), c = 12.4417(2) ? ?= 62.255(0), ?= 79.097(2), ?= 86.764(2)? V = 1378.52(6) ?, Z = 2, Mr = 719.835, Dc = 1.734 g/cm3, F(000) = 714, (MoK) = 3.739 mm-1, T = 293(2) K, final R = 0.0594 and wR = 0.1416 for 2943 observed reflections with I > 2.0(I). The structure of Cu(C13H9N3O2Br)2H2O has been determined by X-ray analysis and revealed that two L-1 ligands coordinate to the copper(Ⅱ) ion through two oxygen and two nitrogen atoms from the hydrazine groups and two pyridine nitrogen atoms to form an elongated and distorted square-bipyramidal environment for Cu(Ⅱ). The complex is also characterized by 1H NMR
