The reaction of [HN(n-C4H9)3]3[WV (CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,...The reaction of [HN(n-C4H9)3]3[WV (CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV (CN)8]{·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]{·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants α=10.397(2) ?, b=11.321(2) ?, c=12.295(3) ? and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) ?, b=13.784(3) ?, c=13.225(3) ?, β=93.44(3)° and Z=4. In complex 1, each [WIV (CN)8]4? unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN? ions forming wavelike alternating-W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV (CN)8]4? ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN? ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ mode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnII ions, while complex 2 exhibits a weak ferromagnetic interaction between CuII ions.展开更多
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
Four new transition metal complexes, [Mn（4,4′-bip）2（OH2）4]（DBA）-4H2O 1 （4,4′-hip = 4,4′-bipyridine, H2DBA = benzene-1,3-dicarboxylic acid） and [M（OH2）（HDPA）2]-3H2O （M = Mn 2, M = Co 3, M = Ni 4, H2DPA ...Four new transition metal complexes, [Mn（4,4′-bip）2（OH2）4]（DBA）-4H2O 1 （4,4′-hip = 4,4′-bipyridine, H2DBA = benzene-1,3-dicarboxylic acid） and [M（OH2）（HDPA）2]-3H2O （M = Mn 2, M = Co 3, M = Ni 4, H2DPA = 2,6-pyridine-dicarboxylic acid）, have been prepared from the reaction of transition metals and carboxylic acids, and characterized by X-ray and elemental analyses. For compound 1, the packing diagram shows that a three-dimensional network is formed via hydrogen bonds and strong π-πinteractions. For compounds 2, 3 and 4, a double-helical chain is formed through hydrogen bonds. Moreover, a three-dimensional network is constructed from chains via complicated hydrogen bonds between crystal water molecules and oxygen atoms of HDPA^-.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
The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nE...The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis （TGA） and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533（17）, b = 8.3408（13）, c = 16.714（3） A^°, β = 101.295（4）°, V = 1494.3（4） A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper（Ⅱ） complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C（10）-H（10）…O（3） and C（13）- H（13）…O（3）, an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.展开更多
基金Supported by the National Natural Science Foundation of China (Nos. 20221101, 20490210, and 20701039)the National Basic Research Program of China (No. 2006CB601102)
文摘The reaction of [HN(n-C4H9)3]3[WV (CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV (CN)8]{·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]{·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants α=10.397(2) ?, b=11.321(2) ?, c=12.295(3) ? and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) ?, b=13.784(3) ?, c=13.225(3) ?, β=93.44(3)° and Z=4. In complex 1, each [WIV (CN)8]4? unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN? ions forming wavelike alternating-W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV (CN)8]4? ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN? ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ mode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnII ions, while complex 2 exhibits a weak ferromagnetic interaction between CuII ions.
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The work was supported by Liaocheng University (31801) and Porf. Dou Jian-Min
文摘Four new transition metal complexes, [Mn（4,4′-bip）2（OH2）4]（DBA）-4H2O 1 （4,4′-hip = 4,4′-bipyridine, H2DBA = benzene-1,3-dicarboxylic acid） and [M（OH2）（HDPA）2]-3H2O （M = Mn 2, M = Co 3, M = Ni 4, H2DPA = 2,6-pyridine-dicarboxylic acid）, have been prepared from the reaction of transition metals and carboxylic acids, and characterized by X-ray and elemental analyses. For compound 1, the packing diagram shows that a three-dimensional network is formed via hydrogen bonds and strong π-πinteractions. For compounds 2, 3 and 4, a double-helical chain is formed through hydrogen bonds. Moreover, a three-dimensional network is constructed from chains via complicated hydrogen bonds between crystal water molecules and oxygen atoms of HDPA^-.
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funded by Guangxi Science Foundation (No. 0731053)Innovation Project of Guangxi Graduate Education of China (No. 2007106020703M62)
文摘The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis （TGA） and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533（17）, b = 8.3408（13）, c = 16.714（3） A^°, β = 101.295（4）°, V = 1494.3（4） A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper（Ⅱ） complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C（10）-H（10）…O（3） and C（13）- H（13）…O（3）, an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.
