Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇...Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇-bipyridine（bpy） and C12H10N2 = 4,4＇-bipyridinylethane（bpe）） have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078（4）, b = 22.4974（10）, c = 20.6272（9） V = 4505.0（3）3, Mr = 454.51, Dc. = 1.340 g·cm^-3, μ = 0.09 mm-1, F（000） = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944（6）, b = 9.820（2）, c = 22.643（5） , V = 5048.4（18）3, Mr = 480.54, Dc. = 1.265 g cm^–3, μ = 0.084 mm^–1, F（000） = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional（2D） layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.展开更多
Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）,...Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）, respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752（12）, b = 7.9126（16）, c = 9.4492（19） ？, α = 97.49（3）, β = 107.71（3）, γ = 94.52（3）o, V = 404.62（14） A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F（000） = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093（3）, b = 7.7665（16）, c = 18.414（4） A, β = 113.36（3）o, V = 2244.1（8） A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F（000） = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4？-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4？-bipy H22＋, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.展开更多
The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structu...The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2 units. The copper atom,located on the crystallographic twofold axis,is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions,and two dihydrogen phosphate oxygen atoms at the axial positions,forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca . 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm,respectively. The two-dimensional networks are stacked parallelly on each other along c -axis to give an extended three-dimensional channel network with an interlayer distance of ca . 0.5030 nm. Crystal data: triclinic,space group P -_1,a =1.0253(2) nm,b =1.4501(3) nm,c =0.79715(16) nm, α =97.91(3)°,β = 90.99(3)° ,γ =85.54(3)°,V =1.1703(4) nm 3,Z =2,R =0.0892,wR =0.2451.展开更多
There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this produ...There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this product via the oxidation of 4,4′ bismethyl 2,2′ bipyridine, followed by esterification and reduction. The yield increases and the reaction conditions become genial in contrast to those of other methods. The molecular structure of the final product was confirmed by means of elemental analysis, IR, 1H NMR and MS spectra.展开更多
基金supported by the National Natural Science Foundation of China(No.21176246)Jiangsu Qinglan Project
文摘Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇-bipyridine（bpy） and C12H10N2 = 4,4＇-bipyridinylethane（bpe）） have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078（4）, b = 22.4974（10）, c = 20.6272（9） V = 4505.0（3）3, Mr = 454.51, Dc. = 1.340 g·cm^-3, μ = 0.09 mm-1, F（000） = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944（6）, b = 9.820（2）, c = 22.643（5） , V = 5048.4（18）3, Mr = 480.54, Dc. = 1.265 g cm^–3, μ = 0.084 mm^–1, F（000） = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional（2D） layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.
基金supported by the National Natural Science Foundation of China(No.21571094)
文摘Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）, respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752（12）, b = 7.9126（16）, c = 9.4492（19） ？, α = 97.49（3）, β = 107.71（3）, γ = 94.52（3）o, V = 404.62（14） A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F（000） = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093（3）, b = 7.7665（16）, c = 18.414（4） A, β = 113.36（3）o, V = 2244.1（8） A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F（000） = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4？-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4？-bipy H22＋, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.
文摘The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2 units. The copper atom,located on the crystallographic twofold axis,is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions,and two dihydrogen phosphate oxygen atoms at the axial positions,forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca . 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm,respectively. The two-dimensional networks are stacked parallelly on each other along c -axis to give an extended three-dimensional channel network with an interlayer distance of ca . 0.5030 nm. Crystal data: triclinic,space group P -_1,a =1.0253(2) nm,b =1.4501(3) nm,c =0.79715(16) nm, α =97.91(3)°,β = 90.99(3)° ,γ =85.54(3)°,V =1.1703(4) nm 3,Z =2,R =0.0892,wR =0.2451.
基金Supported by the National Natural Science Foundation of China(No. 2 0 16 2 0 0 5 ) the Foundation of EducationMinistry(No. 2 0 0 1- 3) .
文摘There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this product via the oxidation of 4,4′ bismethyl 2,2′ bipyridine, followed by esterification and reduction. The yield increases and the reaction conditions become genial in contrast to those of other methods. The molecular structure of the final product was confirmed by means of elemental analysis, IR, 1H NMR and MS spectra.
