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,Structure and Characterization of Three Metal Molybdate Hydrates: Fe(H2O)2(MoO4)2·H3O,NaCo2(MoO4)2(H3O2)and Mn2(MoO4)3·2H3O

Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

State of uranyl silicates MII(HSiUO6)2 ·6H2O (MII=Mn, Co, Ni, Cu, Zn) in aqueous solutions

Uranyl silicates with formula M^II(HSiUO₆)₂·6H₂O (M^II=Mn, Co, Ni, Cu, Zn) were investigated in aqueous solutions in the pH range of 0÷14. The pH interval was established where compounds preserve their composition and structure. It varies in the pH range of (3.5–4.0)÷(10.8–11.4) and depends on M^II type. Out of this pH interval investigated uranyl silicates convert to the compounds of other composition and structure, such as amorphous silica, polyuranates and hydroxides of 3d-transition elements. The solubility of M^II(HSiUO₆)₂·6H₂O was determined, it’s value changes on the several orders of magnitude from 10^?6 M in subalkali solutions to 10^?3 M in acid and strongly alkaline media. Using obtained experimental data the solubility products and solubility curves of uranyl silicates were calculated by mathematical modeling. Also the speciation diagrams of uranium (VI), silicon (IV) and M (II) in solutions and solids were plotted.     

Study of the state of uranogermanates MII(HGeUO6)2·6H2O in Aqueous Solutions (MII = Mn, Co, Ni, Cu, Zn)

The state of d-elements uranogermanates M^II(HGeUO₆)₂·6H₂O in aqueous salt solutions in a wide range of ionic strength, ionic composition, and acidity has been investigated. The pH ranges of the uranogermanates stability have been determined, and products of their transformation have been identified. Solubility, solubility equilibrium constant, and Gibbs energy of formation have been determined for the studied uranogermanates. Diagrams of uranium(VI), germanium(IV), and M(II) state in aqueous solutions and in equilibrium solid phases have been plotted.     

Synthesis, Properties and Crystal Structure of a Novel Coordinated Polymer: {(H2en)(H3O)[(BiPb(C2O4)4(H2O)2)]·2(H2O)}n

A novel oxalate compound {(H2en)(H3O)[BiPb(C2O4)4(H2O)2]·2(H2O)}n 1 (en = ethylenediamine) containing lead and bismuth has been synthesized by hydrothermal methods, and structurally characterized by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P21/c with a = 11.6160(1), b = 12.7426(1), c = 15.5683(5) (A), β = 108.442(4)°, BiPbC10N2O21H21, Mr = 921.46, V = 2186.0(4) (A)3, Z = 4, Dc = 2.800 g/cm3, F(000) = 1712 and μ(MoKα) = 15.837 mm-1. The final R = 0.0502 and wR = 0.1261 for 3391 observed reflections with I > 2(σI). The title com- pound consists of 2-D polyanions and protonized organic amine cations, and they are combined to each other by static attractive force and H-bonds to form the so-called organic-inorganic hybrid material.     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

K3[Fe3.26V0.74(OH)O(PO4)4(H2O)2]·2H2O: a synthetic leucophosphite

A new iron(III)/vanadium(III) phosphate, K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O (1), has been obtained by hydrothermal synthesis and characterized by single crystal X-ray diffraction, Scanning electron microscopy–energy dispersive X-ray spectroscopy, Inductively coupled plasma atomic emission spectroscopy (ICP), thermogravimetric analysis, and FTIR spectroscopy. Single crystal X-ray diffraction reveals a 3D open framework (monoclinic, space group P2₁/n, a?=?9.6391(7)?Å, b?=?9.8063(7)?Å, c?=?9.7268(7)?Å, β?=?100.71(1)°, and V?=?903.38(11)?ų). This structure presents Fe^III and V^III in a 4.4?:?1?M ratio with the metal ions in two different crystallographic sites. Both metallic centers have distorted octahedral environments, linked by PO₄ tetrahedra, forming channels along the a-axis. The asymmetric unit of K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O presents a {M₄(OH)O(PO₄)₄(H₂O)₂}^3? anionic entity, charge balanced by three K⁺, which are located within the channels. It is also possible to distinguish M₄O₂ units whose M^III polyhedra are linked by vertex and edges.     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n · n H2O

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Copper(Ⅱ) Complex [Cu4O4(phen)4(ClC6H4COO)2(H2O)2]·(H2O)3

The title complex of copper(Ⅱ) with m-chlorobenzoic acid, 1,10-phenanthroline (phen) and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group P, a = 1.06853(12), b = 1.30740(16), c = 1.49546(17) nm, α = 101.791(2), β = 103.413(2), γ = 105.815(2)o, V = 1.8736(4) nm3, Mr = 904.67, Dc = 1.604 g/cm3, Z = 2, F(000) = 924, μ = 1.34 mm-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three water molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.     

Isodimorphism of the salts 2RbCl · MIICl2 · 2H2O (MII = Mn,Fe, Co,Cu)

The three-component systems RbClMnCl₂H₂O, 2RbCl · CoCl₂ · 2H₂O2RbCl · CuCl₂ · 2H₂OH₂O, 2RbCl · CoCl₂ · 2H₂O2RbCl · MnCl₂ · 2H₂OH₂O have been studied at 25°C. In the 2RbCl · CoCl₂ · 2H₂O2RbCl · CuCl₂ · 2H₂OH₂O system, a discontinuous series of mixed crystals is formed and in the 2RbCl · CoCl₂ · 2H₂O2RbCl · MnCl₂ · 2H₂OH₂O system, a continuous series is present.The unit cell parameters of the 2RbCl · CoCl₂ · 2H₂O double salt were determined: a = 5.586(2) Å, b = 6.469(3) Å, c = 6.988(2) Å, α = 65.31(3)°, β = 87.69(3)°, γ = 84.65(4)°, volume 228.4 ų, Z = 1.The results obtained and discussed in conjunction with the crystal structure data suggest that for 2M^ICl · M^IICl₂ · 2H₂O type salts the triclinic structure is stable only when the large rubidium and cesium ions participate in combinations with non-Jahn-Teller metal(II) ions. In the cases of Jahn-Teller metal(II) ions or with potassium or ammonium ions a tetragonal structure is always stable.     

Synthesis and crystal structure of a novel tartrate copper(II) two-dimensional coordination polymer: {[Cu2(C4H4O6)2(H2O)2]·4H2O}∞

A new 2D coordination polymer, {[Cu₂(C₄H₄O₆)₂(H₂O)₂]·4H₂O}_∞ has been synthesized by the hydrothermal method and characterized by X-ray single crystal diffraction. Every copper(II) atom adopts a distorted octahedral geometry and coordinates with six oxygen atoms from one water molecule and three tartrate acid ions. The two tartrate acid ions have different coordination modes, one provides four oxygen atoms to coordinate with Cu(II) and another coordinates with all six oxygen atoms. Such a coordination mode generates a two-dimensional coordination polymer. In the solid state, the title compound forms a 3D network structure through hydrogen bonds.     

α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis,characterization, and magnetism of Cu2(phen)4(GeW12O40) and [Ni2(bpy)4(H2O)2(GeW12O40)]⋅2H2O

Two new α-Keggin polyoxometalates, [Cu₂(phen)₄(GeW₁₂O₄₀)] (1) and [Ni₂(bpy)₄(H₂O)₂(GeW₁₂O₄₀)]·2H₂O (2) (phen?=?1,10-phenanthroline, bpy?=?2,2′-bipyridine), have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, single-crystal X-ray diffraction, and magnetic properties. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, and 1 is assembled into two-dimensional (2-D) layers parallel to (1?0?1) based on the adjacent phen π···π stacking interactions (3.788(8)?Å). Variable temperature magnetic measurements show ferromagnetic behavior from 300 to 2?K. Compound 2 crystallizes in the triclinic system, space group P-1, and 2 is assembled into 2-D layers parallel to (1?0?1) based on the adjacent bpy π···π stacking interactions (3.07?Å). Variable temperature magnetic measurements show a weak ferromagnetic behavior from 300 to 26?K followed by antiferromagnetic behavior below 26?K.     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

A diruthenium soft ferromagnet showing T(c) = 3.0 K: Mn4(H2O)16H[Ru2(CO3)4]2[Ru2(CO3)4(H2O)2]·11H2O

A three-dimensional CO(3)(2-)-bridged Mn(II)-Ru(2)(II,III) complex, Mn(4)(H(2)O)(16)H[Ru(2)(CO(3))(4)](2)[Ru(2)(CO(3))(4)(H(2)O)(2)]·11H(2)O (1), was synthesized by self-assembling Ru(2)(CO(3))(4)(3-) paddle-wheel precursors and Mn(2+) cations. It contains an unprecedented layer [Ru(2)(CO(3))(4)](n)(3n-) with (4,4) network. The ferromagnetic coupling between spin centers results in ordering below 3.0 K.