The by products from the dehydration of exo 2 camphanol in the camphor manufacture by hydration process contains two unknown components: A in 14% and B in 15%. The sample mixture containing 90% A and B with different ...The by products from the dehydration of exo 2 camphanol in the camphor manufacture by hydration process contains two unknown components: A in 14% and B in 15%. The sample mixture containing 90% A and B with different mass ratio(ca. 1∶1, 1∶2 and 1∶4) were collected by further fine fractional distillation with 60 plate number for spectroscopic characterization. The combined spectral results of GC, MS and 13 C NMR of the samples revealed that A is exo 2,2,3 trimethylbicyclo[2,2,1]heptane(exo isocamphane) and B is endo 2,2,3 trimethylbicyclo[2,2,1]heptane(endo isocomphane).展开更多
The title complex [Zn（HPDB）2（H2O）2]n·2nDMSO·2nH2O（H2-PDB is pyridine-3, 4-dicarboxylic acid and DMSO the dimethyl sulphoxide） was synthesized under traditional solution condition. Its crystal （C18H28N...The title complex [Zn（HPDB）2（H2O）2]n·2nDMSO·2nH2O（H2-PDB is pyridine-3, 4-dicarboxylic acid and DMSO the dimethyl sulphoxide） was synthesized under traditional solution condition. Its crystal （C18H28N2O14S2Zn） belongs to monoclinic system, space group P21/c with a = 8.2791 （6）, b = 12.5495（10）, c = 13.6519（ 11 ）A°, β = 105.294（2）°, V = 1368.18（18）A°^3, Z = 2, Mr = 625.91, Dx = 1.514 g/cm^3,μ = 1.117 mm^-1, F（000） = 648, R = 0.0654 and wR = 0.1654 for 2414 observed reflections （I 〉 2σ（I））. It has a 2-D planar network, in which the Zn atom is six-coordinated and hydrogen bonds between carboxylate groups, DMSO and water molecules result in the final 3D structure.展开更多
The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crys...The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.4827（2）, b = 11.9086（2）, c = 13.77350（10） A, α = 80.6830（10）, β = 66.6480（10）, γ = 64.048000）°, V = 1554.63（4） A^3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm^3,μ = 0.845 mm^-1, F（000） = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections （1 〉 2σ（I））. The compound contains a six-coordinated copper（Ⅱ） center, which is surround by four N atoms of two phen ligands （Cu-N distances in the range of 1.997（2）- 2.225（2） A）, one sulfate O atom （Cu-O = 2.0037（17） A） and one water O atom （Cu-O（Sw） = 2.719（2） A,） in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.展开更多
We investigated the hydrolysis of TiⅣ along with naturally abundant AlⅢ ions and reported the formation of a stable and semiconducting nanocluster. Interestingly, this compound exhibits an unusual odd-membered ring ...We investigated the hydrolysis of TiⅣ along with naturally abundant AlⅢ ions and reported the formation of a stable and semiconducting nanocluster. Interestingly, this compound exhibits an unusual odd-membered ring structure and also represents the largest Al-containing polyoxotitanium cluster(PTC) observed thus far. The presence of a shell of organic ligands as well as the incorporation of hetero-AlⅢ ions endowed the nanocluster with high air, thermal, and pH stabilities. The present compound exhibited a record photocatalytic hydrogen evolution of 402.88 μmol g–1 h–1 among PTC materials. This work not only paves the way towards stable PTC materials but also provides new insights into the design of novel photocatalysts.展开更多
The title compounds Mo3S4(dtp)3(o-CH3OC6H4COO)(Py) 1 and Mo3S(dtp)3(p-HOC6H4COO)(DMF)稥tOH 2 (dtp = diethyldithiophosphate) were synthesized by thereactions of Mo3S4(dtp)4(CH3CN) and Mo3S4(dtp)3(CH2ClCOO)(Py) with o-m...The title compounds Mo3S4(dtp)3(o-CH3OC6H4COO)(Py) 1 and Mo3S(dtp)3(p-HOC6H4COO)(DMF)稥tOH 2 (dtp = diethyldithiophosphate) were synthesized by thereactions of Mo3S4(dtp)4(CH3CN) and Mo3S4(dtp)3(CH2ClCOO)(Py) with o-methoxylbenzoic acid and p-hydroxybenzoic acid, respectively. Their crystal structures were determined by X-ray diffraction analysis. The crystal data for compound 1: Mo3S10P3C25H42O9N, monoclinic P21/n, Mr = 1201.93, Z = 4, a = 14.164(1), b = 23.065(2), c = 14.732(1) ? = 109.677(1) ? V = 4532(1) ?, D= 1.762 gcm-3, = 1.428 mm-1, F (000) = 2408, R = 0.0739, wR = 0.1528 for 3552 observed reflections (I > 2); and for compound 2: Mo3S10P3C24H48O11N, triclinic P ? Mr = 1227.96, Z = 2, = 10.2098(3), b = 14.3333(4), c = 18.1711(5) ? = 94.694(1), = 102.166(1), = 110.665(1) , V = 2396.5(1)3, Dc = 1.638 gcm-3, = 1.350mm-1, F (000) = 1184, R = 0.0445, wR = 0.1281 for 6597 observed reflections (I > 2). Intermolecular S…S interactions are observed between the molecules of compound 1 while intramolecular O…HC and intermolecular S…HC hydrogen bondings are found in the crystal packing diagram of compound 2.展开更多
The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its st...The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pi with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6) ? a = 79.5990(10), = 83.6300(10), ? = 71.8280(10)o, V = 1272.60(8) ?, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2s(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4?-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.展开更多
A stable organometallic Pd (Ⅱ) compound Pd(ptac-C,N)(acac-O,O) (Hacac = acetyl acetone, Hptac = 3-(2-pyridinethioxy)-acac, formula: C15H17NO4SPd, Mr = 413.76) 1 has been synthesized and its crystal structure was dete...A stable organometallic Pd (Ⅱ) compound Pd(ptac-C,N)(acac-O,O) (Hacac = acetyl acetone, Hptac = 3-(2-pyridinethioxy)-acac, formula: C15H17NO4SPd, Mr = 413.76) 1 has been synthesized and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic with space group C2/c, a = 17.9342(3), b = 17.7791(4), c = 13.1800(1) ? b = 128.400(1), V = 3293.5(1) 3, Z = 8, Dc = 1.669 g/cm3, F(000) = 1664, m = 1.269 mm-1, R = 0.0261 and wR = 0.0710 for 2653 observed reflections (I > 2s(I)). There exist two Pd rings in the title compound, C(14)O(4)PdO(3)C(12)C(13) and C(1)NPdC(8)S, with the palladium atom taking a square-planar coordination. Two oxygen atoms from the acetyl acetone ligand (PdO, 1.991(2) and 2.036(2) ), one N atom (PdN 2.019 ? and the g-carbon atom (PdC 2.067(3) ? from the ptac ligand are coordinated to Pd.展开更多
A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure h...A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure has been determined by X-ray crystallography and the data for the title compound: Mo4S14P6O14C24H60, triclinic P , Mr = 1591.14, a = 12.5596(5), b = 14.3441(5), c = 18.0005(6) ? = 85.318(1), = 70.495(1), = 78.415(2)? V = 2994.2(2) ?, Z = 2, Dc = 1.765 g/cm3, (MoK? = 1.515 mm-1, F(000) = 1596, R = 0.0918 and wR = 0.1908 for 3546 reflections (I > 2(I)). X-ray analysis reveals that two weak CH贩稯 hydrogen bonds exist in the packing diagram with C贩稯 distance 3.22(5) ? The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.展开更多
A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belong...A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.展开更多
A new compound [Zn3（C7NO4H3）3Cl4]·[C6NO2H6]4·4H2O （I） has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018（14）,b=12...A new compound [Zn3（C7NO4H3）3Cl4]·[C6NO2H6]4·4H2O （I） has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018（14）,b=12.6902（10）,c=25.1170（2）,β=90.54°,V=5387.0（8）3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F（000）=2840,μ（MoKa）=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections （I 〉 2σ（I））.Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.展开更多
文摘The by products from the dehydration of exo 2 camphanol in the camphor manufacture by hydration process contains two unknown components: A in 14% and B in 15%. The sample mixture containing 90% A and B with different mass ratio(ca. 1∶1, 1∶2 and 1∶4) were collected by further fine fractional distillation with 60 plate number for spectroscopic characterization. The combined spectral results of GC, MS and 13 C NMR of the samples revealed that A is exo 2,2,3 trimethylbicyclo[2,2,1]heptane(exo isocamphane) and B is endo 2,2,3 trimethylbicyclo[2,2,1]heptane(endo isocomphane).
基金This work was supported by the State Key Basic Research and Development Plan of China (001CB108906), the NNSF of China (No. 20173063) and NSF of Fujian Province (E0020001)
文摘The title complex [Zn（HPDB）2（H2O）2]n·2nDMSO·2nH2O（H2-PDB is pyridine-3, 4-dicarboxylic acid and DMSO the dimethyl sulphoxide） was synthesized under traditional solution condition. Its crystal （C18H28N2O14S2Zn） belongs to monoclinic system, space group P21/c with a = 8.2791 （6）, b = 12.5495（10）, c = 13.6519（ 11 ）A°, β = 105.294（2）°, V = 1368.18（18）A°^3, Z = 2, Mr = 625.91, Dx = 1.514 g/cm^3,μ = 1.117 mm^-1, F（000） = 648, R = 0.0654 and wR = 0.1654 for 2414 observed reflections （I 〉 2σ（I））. It has a 2-D planar network, in which the Zn atom is six-coordinated and hydrogen bonds between carboxylate groups, DMSO and water molecules result in the final 3D structure.
文摘The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.4827（2）, b = 11.9086（2）, c = 13.77350（10） A, α = 80.6830（10）, β = 66.6480（10）, γ = 64.048000）°, V = 1554.63（4） A^3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm^3,μ = 0.845 mm^-1, F（000） = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections （1 〉 2σ（I））. The compound contains a six-coordinated copper（Ⅱ） center, which is surround by four N atoms of two phen ligands （Cu-N distances in the range of 1.997（2）- 2.225（2） A）, one sulfate O atom （Cu-O = 2.0037（17） A） and one water O atom （Cu-O（Sw） = 2.719（2） A,） in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.
文摘We investigated the hydrolysis of TiⅣ along with naturally abundant AlⅢ ions and reported the formation of a stable and semiconducting nanocluster. Interestingly, this compound exhibits an unusual odd-membered ring structure and also represents the largest Al-containing polyoxotitanium cluster(PTC) observed thus far. The presence of a shell of organic ligands as well as the incorporation of hetero-AlⅢ ions endowed the nanocluster with high air, thermal, and pH stabilities. The present compound exhibited a record photocatalytic hydrogen evolution of 402.88 μmol g–1 h–1 among PTC materials. This work not only paves the way towards stable PTC materials but also provides new insights into the design of novel photocatalysts.
基金① This work was financially supported by the NNSF of China (No. 29733090 and No. 20173063)Key Project in KIP of CAS (KJCX2-H3) the NNSF of Fujian Province (E0020001)
文摘The title compounds Mo3S4(dtp)3(o-CH3OC6H4COO)(Py) 1 and Mo3S(dtp)3(p-HOC6H4COO)(DMF)稥tOH 2 (dtp = diethyldithiophosphate) were synthesized by thereactions of Mo3S4(dtp)4(CH3CN) and Mo3S4(dtp)3(CH2ClCOO)(Py) with o-methoxylbenzoic acid and p-hydroxybenzoic acid, respectively. Their crystal structures were determined by X-ray diffraction analysis. The crystal data for compound 1: Mo3S10P3C25H42O9N, monoclinic P21/n, Mr = 1201.93, Z = 4, a = 14.164(1), b = 23.065(2), c = 14.732(1) ? = 109.677(1) ? V = 4532(1) ?, D= 1.762 gcm-3, = 1.428 mm-1, F (000) = 2408, R = 0.0739, wR = 0.1528 for 3552 observed reflections (I > 2); and for compound 2: Mo3S10P3C24H48O11N, triclinic P ? Mr = 1227.96, Z = 2, = 10.2098(3), b = 14.3333(4), c = 18.1711(5) ? = 94.694(1), = 102.166(1), = 110.665(1) , V = 2396.5(1)3, Dc = 1.638 gcm-3, = 1.350mm-1, F (000) = 1184, R = 0.0445, wR = 0.1281 for 6597 observed reflections (I > 2). Intermolecular S…S interactions are observed between the molecules of compound 1 while intramolecular O…HC and intermolecular S…HC hydrogen bondings are found in the crystal packing diagram of compound 2.
基金This work was financially supported by the NNSFC (No. 20173063) the State Key Basic Research and Development Plan of China (001CB108906) and the NSF of Fujian Province (E0020001)
文摘The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pi with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6) ? a = 79.5990(10), = 83.6300(10), ? = 71.8280(10)o, V = 1272.60(8) ?, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2s(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4?-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.
基金the State Key Basic Research and Development Plan of China (001CB108906), the NNSF of China (No. 29733090 and No. 20173063), Key Project in KIP of CAS (KJCX2-H3) and the NSF of Fujian province (E0020001)
文摘A stable organometallic Pd (Ⅱ) compound Pd(ptac-C,N)(acac-O,O) (Hacac = acetyl acetone, Hptac = 3-(2-pyridinethioxy)-acac, formula: C15H17NO4SPd, Mr = 413.76) 1 has been synthesized and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic with space group C2/c, a = 17.9342(3), b = 17.7791(4), c = 13.1800(1) ? b = 128.400(1), V = 3293.5(1) 3, Z = 8, Dc = 1.669 g/cm3, F(000) = 1664, m = 1.269 mm-1, R = 0.0261 and wR = 0.0710 for 2653 observed reflections (I > 2s(I)). There exist two Pd rings in the title compound, C(14)O(4)PdO(3)C(12)C(13) and C(1)NPdC(8)S, with the palladium atom taking a square-planar coordination. Two oxygen atoms from the acetyl acetone ligand (PdO, 1.991(2) and 2.036(2) ), one N atom (PdN 2.019 ? and the g-carbon atom (PdC 2.067(3) ? from the ptac ligand are coordinated to Pd.
基金This work was financially supported by the NNSF of China (No. 29733090 and No. 20173063) Key Project in KIP of CAS (KJCX2-H3) and the NNSF of Fujian Province (E0020001)
文摘A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure has been determined by X-ray crystallography and the data for the title compound: Mo4S14P6O14C24H60, triclinic P , Mr = 1591.14, a = 12.5596(5), b = 14.3441(5), c = 18.0005(6) ? = 85.318(1), = 70.495(1), = 78.415(2)? V = 2994.2(2) ?, Z = 2, Dc = 1.765 g/cm3, (MoK? = 1.515 mm-1, F(000) = 1596, R = 0.0918 and wR = 0.1908 for 3546 reflections (I > 2(I)). X-ray analysis reveals that two weak CH贩稯 hydrogen bonds exist in the packing diagram with C贩稯 distance 3.22(5) ? The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.
基金This work was supported by the State Key Basic Research and Development Plan of China (001CB108906)the YIF (2005J060) and NSF (2006J0015) of Fujian Provincethe Major Special Foundation of Fujian Province (2005HZ1027 and 2005HZ01-1)
文摘A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.
基金supported by the Natural Science Foundation of Fujian Province (2006F3042)
文摘A new compound [Zn3（C7NO4H3）3Cl4]·[C6NO2H6]4·4H2O （I） has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018（14）,b=12.6902（10）,c=25.1170（2）,β=90.54°,V=5387.0（8）3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F（000）=2840,μ（MoKa）=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections （I 〉 2σ（I））.Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.
