Yue-Qing Zheng

New catenary coordination polymers using fumarato ligand as bridging spacer: crystal structures of [Mn(phen)2(H2O)2]L·4H2O, Mn(phen)(H2O)2L and Zn(phen)L·H2L with H2L=fumaric acid

Abstract Reactions of freshly precipitated MnCO3·xH2O and ZnCO3·yH2O with phen and fumaric acid (H2L) in EtOH/H2O afforded [Mn(phen)2(H2O)2]L·4H2O 1, Mn(phen)(H2O)2L 2 and Zn(phen)L·H2L 3, respectively. Compound 1 consists of [Mn(phen)2(H2O)2]2+ complex cations, fumarate anions and crystal H2O molecules. The complex cations are assembled by intermolecular π–π stacking interactions into 2D layers, between which the fumarate anions and crystal H2O molecules form hydrogen bonded 2D open network. Within the complex 2, the [Mn(phen)(H2O)2]2+ moieties are bridged by bis–monodentate fumarato ligands to generate 1D zigzag chains, which are assembled into 2D layers by weak C–H⋯O hydrogen bonds. The complex 3 is composed of fumaric molecules and 1D zigzag ∞ 1 [ Zn(phen)L 2 / 2 ] polymeric chains resulting from the [Zn(phen)]2+ moieties interlinked by bis–monodentate fumarato ligands. The polymeric chains and fumaric molecules are held together via significant π–π stacking interactions between the fumaric plane and pendant phen to form 2D layers, which are further assembled by interlayer O–H⋯O hydrogen bonds between hydroxyl group and non-coordinating fumarato O atom.

Syntheses and crystal structures of copper(II) complexes derived from 2,4,6-tris(2-pyridyl)-1,3,5-triazine

Treatment of freshly precipitated Cu(OH)2 · xH2O and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with oxalic and malonic acids in methanol-water at room temperature gave [Cu(tptz)(C2O4)(H2O)] · 4H2O (1) and [Cu(pma)(C3H2O4)(H2O)] · H2O (2) (pma = 2-aminocarbonylpyridine), respectively. Reaction in the absence of any acid resulted in [Cu(bpca)(tca)] · 2H2O (3) (bpca = bis(2-pyridylcarbonyl)amide anion; tca = 2-pyridinecarboxylate anion). Complex 1 consists of [Cu(tptz)(C2O4)(H2O)] and lattice H2O molecules; the tridentate tptz ligand, bidentate oxalate dianion and an aqua ligand are bound to Cu with distorted octahedral geometry. Complex 2 is composed of [Cu(pma)(C3H2O4)(H2O)] and lattice H2O molecules; the bidentate 2-aminocarbonylpyridine ligand, a bidentate malonate dianion and an aqua ligand are coordinated to Cu with a slightly distorted square pyramidal geometry. Complex 3 consists of [Cu(bpca)(tca)] and lattice H2O molecules. Square pyramidally coordinated Cu atoms are surrounded by tridentate bpca with nitrogen donor atoms and a bidentate 2-pyridinecarboxylate anion.

Supramolecular Assemblies via Hydrogen Bonding and π-π Stacking Interactions: Crystal Structures of [Co(phen)(H2O)4]L·0.5H2O and [CO2(phen)2(H2O)2L2] with H2L = Adipic Acid

Reaction of freshly-prepared CoCO3, phenanthroline monohydrate and adipic acid (H2L) in CH3OH/H2O produced a mixture of [Co(phen)(H2O)4]L·0.5H2O (1) and [CO2(phen)2(H2O)2L2] (2). Complex 1 crystallizes in the orthorhombic space group Pbcn with cell dimensions a = 23.380(2), b = 12.347(1), c = 12.821(1) Å, and D calc = 1.390 g/cm3 for Z = 8, and complex 2 in the triclinic space group P1; with cell dimensions a = 8.203(1), b = 9.809(1), c = 11.827(1) Å, α = 70.34(1), β = 74.81(1), γ = 71.54(1)° and D calc = 1.592 g/cm3 for Z = 1. Complex 1 consists of [Co(phen)(H2O)4]2+ complex cations, adipate anions and crystal H2O molecules. The Co atoms are each octahedrally coordinated by one chelating phen ligand and four water molecules with d(Co-O) = 2.041-2.097 Å and d(Co-N) = 2.144, 2.160 Å. Through hydrogen bonds, the [Co(phen)(H2O)4]2+ complex cations and adipate anions are interconnected into 2D layers, whose assembly could be ascribed to weak π-π stacking interactions between interdigitating phen ligands. Complex 2 is composed of centrosymmetric dinuclear [Co2(phen)2(H2O)2L2) molecules, in which the Co atoms are each coordinated by two N atoms of one chelating phen ligand and four O atoms of one H2O molecule and two adipato ligands to form distorted octahedra with d(Co-O) = 2.027-2.248 Å and d(Co-N) = 2.112, 2.162 Å. The centrosymmetric molecules are assembled via intermolecular hydrogen bonds and π-π interactions into 2D layers.

Syntheses and crystal structures of new suberato-bridged Mn(II) phen complexes: {[Mn(phen)2]L2/2}2·H2L·8H2O, {[Mn(phen)(H2O)3]2L}L·2H2L·4H2O and {[Mn(phen)2(HL)]2L}·H2L (H2L=HOOC(CH2)6COOH)

Abstract Three suberato-bridged Mn(II) phen complexes {[Mn(phen)2]L2/2}2·H2L·8H2O (1), {[Mn(phen)(H2O)3]2L}L·2H2L·4H2O (2) and {[Mn(phen)2(HL)]2L}·H2L (3) have been synthesized and structurally characterized by single crystal X-ray diffraction methods. The [Mn(phen)2]2+ moieties in 1 are interlinked by bis-monodentate suberato ligands to generate ∞1[Mn(phen)2L2/2] polymeric chains. Complex 2 features a nanoporous hydrogen bonded framework made up of suberate anions, suberic acid molecules and lattice water molecules with the bis-monodentate suberato bridged dinuclear {[Mn(phen)(H2O)3]2L}2+ complex cations residing in tunnels. The bis-monodentate suberato bridged dinuclear {[Mn(phen)2(HL)]2L} molecules in 3 are assembled into a 3D framework with suberic acid molecules situated in the tunnels.

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O (1) and [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O (2) and one Cu(II) hydroxo glutarate [Cu5(OH)6(C5H6O4)2] · 4H2O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO6} octahedra in “4 + 1 + 1” and “4 + 2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO6} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H2O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO6} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H2O molecules. The {CuO6} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H2O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.

Synthesis and crystal structure of [Zn(H2O)4(C4H2O4)]·H2O

Reaction of freshly prepared Zn(OH)2−2 x (CO3) x ·yH2O with fumaric acid in CH3OH/H2O (1:1 v/v) at room temperature afforded [Zn(H2O)4(C4H2O4)]·H2O. An X-ray structure determination indicates that the title compound consists of hydrogen bonded H2O molecules and polymeric chains, , resulting from Zn atoms bridged by bis-monodentate fumarate anions. The Zn atoms are octahedrally coordinated by six oxygen atoms of four aqua ligands and two different fumarate anions with the carboxylato oxygen atoms in cis positions. Supramolecular assembly of the polymeric chains is due to extensive hydrogen bonding interactions. Thermal analysis shows that [Zn(H2O)4(C4H2O4)]·H2O decomposes in two steps upon heating; initial endothermic dehydration over 45–80°C is followed by decomposition of anhydrous zinc fumarate at 360–825°C.

Self-assemblies of Ni(II) with phenanthroline and maleate anions: [Ni(H2O)3(phen)L] ⋅ H2O (1) and [Ni(H2O)2(phen)L] ⋅ 2H2O (2) with H2L = maleic acid

AbstractThe complex [Ni(H2O)3(phen)(C4H2O4)] ⋅ H2O (1), which was obtained by reaction of phenanthroline, Ni(NO3)2 ⋅ 6H2O, and maleic acid in CH3OH/H2O at pH = 7.05, crystallized in the monoclinic space group P21 (no. 4) with cell dimensions: a = 9.350(1) Å, b = 7.631(1) Å, c = 12.821(1) Å, β = 106.25(1), and Dcalc = 1.607 g/cm3 for Z = 2. The Ni atoms are each octahe drally coordinated by one chelating phen ligand, three H2O molecules and one monodentate maleato ligand to form [Ni(H2O)3(phen)(C4H2O4)] complex molecules with d(Ni–O) = 2.038–2.090 Å, d(Ni–N) = 2.066, 2.089 Å. The formed complex molecules are, via the intermolecular hydrogen bonds, assembled into columnar 1D chains. Interdigitation of the chelating phen ligands of the neighboring chains leads to 2D layers and the crystal H2O molecules are hydrogen bonded to the oxygen atoms of the maleate not coordinated to the Ni atom. However, reaction of NiCO3, phen, and maleic acid in CH3OH/H2O at pH = 6.33 afforded [Ni(H2O)2(phen)(C4H2O4)] ⋅ 2H2O (2), which crystallized in the triclinic space group

Synthesis, crystal structures, and fluorescence properties of (RS)-2-methylglutarato Zn(II), Cd(II) complexes

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