The crystal structure of the title compound [Mn(sapn)(H2O)2]Br (H2sapn = N,N?bis-(salicylidene)-1,3-diaminopropane) with formula C17H18N2O4MnBr and Mr = 449.18 has been determined by X-ray diffraction. The crystal is ...The crystal structure of the title compound [Mn(sapn)(H2O)2]Br (H2sapn = N,N?bis-(salicylidene)-1,3-diaminopropane) with formula C17H18N2O4MnBr and Mr = 449.18 has been determined by X-ray diffraction. The crystal is triclinic with space group P , a = 7.777(1), b = 10.459(2), c = 11.96(3), = 78.22(1), =75.16(8), = 86.80(5)? V = 919(3)3, Dc = 1.631g/cm3, F(000) = 456, = 2.917 cm-1 and Z = 2, with R = 0.0428 and wR = 0.1092 for 2427 reflections (I > 2s(I)). Two nitrogen and two oxygen atoms from the sapn group chelate to the MnⅢ ion, forming a distorted octahedral geometry together with two coordinated water molecules. A bromide anion exists outside as a counter ion.展开更多
The title compound C 17 H 14 O, M r =234.30, is orthorhombic, space group Pbca with unit cell of a=16.410 (2), b=15.451(2), c=10.261(2); Z=8, D c =1.196 g/cm 3; V=2601(1) 3; λ (Mo Kα)=0.71069, μ (Mo Kα ) =0.73 cm...The title compound C 17 H 14 O, M r =234.30, is orthorhombic, space group Pbca with unit cell of a=16.410 (2), b=15.451(2), c=10.261(2); Z=8, D c =1.196 g/cm 3; V=2601(1) 3; λ (Mo Kα)=0.71069, μ (Mo Kα ) =0.73 cm -1 , F (000)=992, final R=0.048, R w =0.053 for 1121 observed reflections with I>3.00σ(I ). As the two phenyl planes and the C 4H 4CO group are non coplanar ,the molecular conjugated system was disturbed.展开更多
N-(5-phenylseleno)pentyl succinimide 1, C15H19NO2Se (Mr = 324.27), was prepared by treating Br(CH2)5SePh with potassium succinimide. Its crystal structure has been determined by X-ray single-crystal diffraction. The c...N-(5-phenylseleno)pentyl succinimide 1, C15H19NO2Se (Mr = 324.27), was prepared by treating Br(CH2)5SePh with potassium succinimide. Its crystal structure has been determined by X-ray single-crystal diffraction. The crystal of 1 belongs to monoclinic system, space group P21/c with the crystal cell parameters: a = 18.018(6), b = 5.980(2), c = 14.682(5) ? = 109.977(6)? V = 1486.7(9) 3, Z = 4, Dc = 1.449 g/cm3, (MoK? = 2.523 mm-1, F(000) = 664,the final R = 0.0302 and wR = 0.0666 for 2623 independent observed reflections with I > 2(I). Structure analyses revealed that there exist strong nonclassical hydrogen bonds (CH…O).展开更多
A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal...A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal structure was determined by X-ray diffraction method. The complex crystallizes in monoclinic, space group P21/n with a = 9.913(4), b = 19.057(8), c = 10.169(4) ? b = 114.292(7), V = 1751(1) 3, C26H38Cu2N8O14, Mr = 813.72, Dc = 1.543 g/cm3, m(MoKa) = 1.290 mm-1, F(000) = 840, Z = 2, the final R = 0.0398 and wR = 0.0986 for 1878 observed reflections (I>2s(I)). The imino nitroxide 2-(2-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl (im2-py) is reduced in the reaction to yield Him2-py which consists of oxalato-bridged centrosymmetric [Cu2(m-C2O4)(Him2-py)2(H2O)2]2+ ions and noncoordinated NO3- anions. Each copper(II) ion is in a distorted tetragonal pyramid environment: two nitrogen atoms from Him2-py and two oxygen atoms from the oxalate group are in the basal plane, and one water molecule at the axial position.展开更多
The efficient synthesis of dimethylhexane-1,6-dicarbamate(HDC)from 1,6-hexanediamine(HDA)and methyl carbonate over a series of heterogeneous catalysts(e.g.,Mg O,Fe2O3,Mo2O3,and Ce O2)was investigated.The reaction path...The efficient synthesis of dimethylhexane-1,6-dicarbamate(HDC)from 1,6-hexanediamine(HDA)and methyl carbonate over a series of heterogeneous catalysts(e.g.,Mg O,Fe2O3,Mo2O3,and Ce O2)was investigated.The reaction pathway was confirmed as an alcoholysis reaction through a series of designed experiments.Under optimized conditions,100%HDA conversion with 83.1%HDCtotaland 16.9%polyurea was obtained using a onestep with high temperature procedure with Ce O2as the catalyst.A new two-step with variable temperature technology was developed based on the reaction pathway to reduce the polyurea yield.Using the proposed method,the HDCtotalyield reached 95.2%,whereas the polyurea yield decreased to 4.8%.The Ce O2catalyst showed high stability and did not exhibit any observable decrease in the HDC yield or any structural changes after four recycling periods.展开更多
The two-component solid forms involving 4,4'-methylene-bis(benzenamine) included both salts and co-crystals,while 4,4'methylene-bis(benzenamine) crystallized exclusively as a salt,in agreement with the differe...The two-component solid forms involving 4,4'-methylene-bis(benzenamine) included both salts and co-crystals,while 4,4'methylene-bis(benzenamine) crystallized exclusively as a salt,in agreement with the differences in the pK a values.Many of the crystal structures displayed either the neutral or the ionic form of the carboxylic acid-amino heterosynthon,and the similarity in crystal structures between the neutral and the ionized molecules makes the visual distinction between a salt and co-crystal dependent on the experimental location of the acidic proton.A variety of supramolecular hydrogen bonded motifs involving interactions between the aza molecules and carboxylic acid groups are observed rather than just the O-H···N/O-H···O motif.The motifs are identical in all the two compounds analyzed showing the robustness of these supramolecular synthons.In all adducts,recognition between the constituents is established through either N-H···O and/or O-H···O/O-H···N pairwise hydrogen bonds.In all adducts,COOH functional groups available on 1 and 2 interact with the N-donor compounds.The COOH moieties in 1 forms only single N-H···O hydrogen bonds,whereas in 2,it forms pairwise O-H···N/N-H···O hydrogen bonds.The supramolecular architectures are elegant and simple,with stacking of networks in 2,but a rather complex network with a threefold interpenetration pattern was found in 1.Thermal stability of these compounds has been investigated by thermogravimetric analysis(TGA) of mass loss.展开更多
The structure [MnmTPP][Me2DCNQI] （TPP = tetraphenylporphinato; Me2DCNQI = 2,5-dimethyl-N,N＇-dicyanoquinonediimine） has been determined from X-ray powder diffraction data. The nonsolvated structure is composed of li...The structure [MnmTPP][Me2DCNQI] （TPP = tetraphenylporphinato; Me2DCNQI = 2,5-dimethyl-N,N＇-dicyanoquinonediimine） has been determined from X-ray powder diffraction data. The nonsolvated structure is composed of linear （I-D） chains of alternating [MnmTPP]＋ and ta-[MezDCNQI]＇- with intrachain Mn...Mn separations of 12.83 A, and a Mn-NDcNQI distance of 2.18A. The dihedral angle between the mean Mn（N4）xpp and [MezDCNQI]＇-planes, and the Mn-（N-C）ocNQ1 angle are 84.18° and 143.6°, respectively. [MnInTpP][MezDCNQI] has a Tc of 4.3 K from the 10 Hz x（T） data, 2-K coercivity of 5,600 Oe, and 6,300 emuOe/mol remnant magnetization that are reduced from that observed for related materials, and their in- clusion extends the magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn（N4）xPp and [TCNE]＇-（TCNE --- tetracyanoethylene） planes and Mn-（N-C）Tcr angles. This is in accord with the in- trachain coupling arising from the overlap of the Mnm dz2-1ike singly occupied molecular orbital （SOMO） and the z component of the [TCNE]- π＊ （π2＊） SOMO, which increases with decreasing dihedral angle between the mean Mn（N4）xep and [TCNE]＇- planes and Mn-（N-C）TcNE angle.展开更多
基金This work was supported by The State Key Basic Research and Development Plan (G1998010100) NNSFC (No. 2973309029973047 and 39970177)
文摘The crystal structure of the title compound [Mn(sapn)(H2O)2]Br (H2sapn = N,N?bis-(salicylidene)-1,3-diaminopropane) with formula C17H18N2O4MnBr and Mr = 449.18 has been determined by X-ray diffraction. The crystal is triclinic with space group P , a = 7.777(1), b = 10.459(2), c = 11.96(3), = 78.22(1), =75.16(8), = 86.80(5)? V = 919(3)3, Dc = 1.631g/cm3, F(000) = 456, = 2.917 cm-1 and Z = 2, with R = 0.0428 and wR = 0.1092 for 2427 reflections (I > 2s(I)). Two nitrogen and two oxygen atoms from the sapn group chelate to the MnⅢ ion, forming a distorted octahedral geometry together with two coordinated water molecules. A bromide anion exists outside as a counter ion.
文摘The title compound C 17 H 14 O, M r =234.30, is orthorhombic, space group Pbca with unit cell of a=16.410 (2), b=15.451(2), c=10.261(2); Z=8, D c =1.196 g/cm 3; V=2601(1) 3; λ (Mo Kα)=0.71069, μ (Mo Kα ) =0.73 cm -1 , F (000)=992, final R=0.048, R w =0.053 for 1121 observed reflections with I>3.00σ(I ). As the two phenyl planes and the C 4H 4CO group are non coplanar ,the molecular conjugated system was disturbed.
基金This work was supported by the NNSFC (No. 29832030)
文摘N-(5-phenylseleno)pentyl succinimide 1, C15H19NO2Se (Mr = 324.27), was prepared by treating Br(CH2)5SePh with potassium succinimide. Its crystal structure has been determined by X-ray single-crystal diffraction. The crystal of 1 belongs to monoclinic system, space group P21/c with the crystal cell parameters: a = 18.018(6), b = 5.980(2), c = 14.682(5) ? = 109.977(6)? V = 1486.7(9) 3, Z = 4, Dc = 1.449 g/cm3, (MoK? = 2.523 mm-1, F(000) = 664,the final R = 0.0302 and wR = 0.0666 for 2623 independent observed reflections with I > 2(I). Structure analyses revealed that there exist strong nonclassical hydrogen bonds (CH…O).
基金This work was supported by the National Natural Science Foundation of China (No. 20271029)
文摘A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal structure was determined by X-ray diffraction method. The complex crystallizes in monoclinic, space group P21/n with a = 9.913(4), b = 19.057(8), c = 10.169(4) ? b = 114.292(7), V = 1751(1) 3, C26H38Cu2N8O14, Mr = 813.72, Dc = 1.543 g/cm3, m(MoKa) = 1.290 mm-1, F(000) = 840, Z = 2, the final R = 0.0398 and wR = 0.0986 for 1878 observed reflections (I>2s(I)). The imino nitroxide 2-(2-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl (im2-py) is reduced in the reaction to yield Him2-py which consists of oxalato-bridged centrosymmetric [Cu2(m-C2O4)(Him2-py)2(H2O)2]2+ ions and noncoordinated NO3- anions. Each copper(II) ion is in a distorted tetragonal pyramid environment: two nitrogen atoms from Him2-py and two oxygen atoms from the oxalate group are in the basal plane, and one water molecule at the axial position.
基金Supported by the Science and Technology Ministry of China(2013BAC11B03)National Nature Science Foundation of China(21476244,21206180,21406245)
文摘The efficient synthesis of dimethylhexane-1,6-dicarbamate(HDC)from 1,6-hexanediamine(HDA)and methyl carbonate over a series of heterogeneous catalysts(e.g.,Mg O,Fe2O3,Mo2O3,and Ce O2)was investigated.The reaction pathway was confirmed as an alcoholysis reaction through a series of designed experiments.Under optimized conditions,100%HDA conversion with 83.1%HDCtotaland 16.9%polyurea was obtained using a onestep with high temperature procedure with Ce O2as the catalyst.A new two-step with variable temperature technology was developed based on the reaction pathway to reduce the polyurea yield.Using the proposed method,the HDCtotalyield reached 95.2%,whereas the polyurea yield decreased to 4.8%.The Ce O2catalyst showed high stability and did not exhibit any observable decrease in the HDC yield or any structural changes after four recycling periods.
基金supported by the National Natural Science Foundation of China(20701023 and 21172127)the Natural Science Foundation of Shandong Province,China(BS2010NJ004, 2009ZRB019KH)
文摘The two-component solid forms involving 4,4'-methylene-bis(benzenamine) included both salts and co-crystals,while 4,4'methylene-bis(benzenamine) crystallized exclusively as a salt,in agreement with the differences in the pK a values.Many of the crystal structures displayed either the neutral or the ionic form of the carboxylic acid-amino heterosynthon,and the similarity in crystal structures between the neutral and the ionized molecules makes the visual distinction between a salt and co-crystal dependent on the experimental location of the acidic proton.A variety of supramolecular hydrogen bonded motifs involving interactions between the aza molecules and carboxylic acid groups are observed rather than just the O-H···N/O-H···O motif.The motifs are identical in all the two compounds analyzed showing the robustness of these supramolecular synthons.In all adducts,recognition between the constituents is established through either N-H···O and/or O-H···O/O-H···N pairwise hydrogen bonds.In all adducts,COOH functional groups available on 1 and 2 interact with the N-donor compounds.The COOH moieties in 1 forms only single N-H···O hydrogen bonds,whereas in 2,it forms pairwise O-H···N/N-H···O hydrogen bonds.The supramolecular architectures are elegant and simple,with stacking of networks in 2,but a rather complex network with a threefold interpenetration pattern was found in 1.Thermal stability of these compounds has been investigated by thermogravimetric analysis(TGA) of mass loss.
基金The structure reported in this paper has been deposited with the Cambridge Crystallographic Data Center as Supplementary Publication CCDC No.870451
文摘The structure [MnmTPP][Me2DCNQI] （TPP = tetraphenylporphinato; Me2DCNQI = 2,5-dimethyl-N,N＇-dicyanoquinonediimine） has been determined from X-ray powder diffraction data. The nonsolvated structure is composed of linear （I-D） chains of alternating [MnmTPP]＋ and ta-[MezDCNQI]＇- with intrachain Mn...Mn separations of 12.83 A, and a Mn-NDcNQI distance of 2.18A. The dihedral angle between the mean Mn（N4）xpp and [MezDCNQI]＇-planes, and the Mn-（N-C）ocNQ1 angle are 84.18° and 143.6°, respectively. [MnInTpP][MezDCNQI] has a Tc of 4.3 K from the 10 Hz x（T） data, 2-K coercivity of 5,600 Oe, and 6,300 emuOe/mol remnant magnetization that are reduced from that observed for related materials, and their in- clusion extends the magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn（N4）xPp and [TCNE]＇-（TCNE --- tetracyanoethylene） planes and Mn-（N-C）Tcr angles. This is in accord with the in- trachain coupling arising from the overlap of the Mnm dz2-1ike singly occupied molecular orbital （SOMO） and the z component of the [TCNE]- π＊ （π2＊） SOMO, which increases with decreasing dihedral angle between the mean Mn（N4）xep and [TCNE]＇- planes and Mn-（N-C）TcNE angle.
