Ba4Ta2O9 oxide prepared from an oxalate-based molecular precursor-characterization and properties.

A novel heterometallic oxalate-based compound, {Ba2(H2O)5[TaO(C2O4)3]HC2O4}·H2O (1), was obtained by using an (oxalato)tantalate(V) aqueous solution as a source of the complex anion and characterized by X-ray single-crystal diffraction, IR spectroscopy, and thermal analysis. Compound 1 is a three-dimensional (3D) coordination polymer with the Ta atom connected to eight neighboring Ba atoms through the oxalate ligands and the oxo oxygen group. Thermal treatment of 1 up to 1200 °C leads to molecular precursor-to-material conversion that yields the mixed-metal γ-Ba4Ta2O9 phase. This high-temperature γ-Ba4Ta2O9 polymorph has the 6H-perovskite structure (space group P6(3)/m), in which the Ta2O9 face-sharing octahedral dimers are interconnected via corners to the regular BaO6 octahedra. To date, γ-Ba4Ta2O9 has never been obtained at room temperature, because of the reduction of symmetry (P6(3)/m → P2(1)/c) that usually occurs during the cooling. Spectroscopic, optical, photocatalytic, and electrical properties of the obtained γ-Ba4Ta2O9 phase were investigated. In addition to the experimental data, an absorption spectrum and band structure of the γ-Ba4Ta2O9 polymorph were calculated using density functional theory.

Single-step preparation of the mixed Ba(II)-Nb(V) oxides from a heteropolynuclear oxalate complex.

A novel oxalate-based complex of the formula {Ba(2)(H(2)O)(5)[NbO(C(2)O(4))(3)]HC(2)O(4)}·H(2)O (1) was prepared from an aqueous solution containing the [NbO(C(2)O(4))(3)](3-) and Ba(2+) entities in the molar ratio 1:2, and characterized by X-ray single-crystal diffraction, IR spectroscopy, and thermal analysis. The crystal packing of 1 reveals a complex three-dimensional (3D) network: the Nb polyhedron is connected to eight neighboring Ba polyhedra through the oxalate ligands and the oxo-oxygen group, whereas the Ba polyhedra share edges and vertices. The ability of compound 1 to act as a single-source precursor for the formation of bimetallic oxides was investigated by the thermal analysis (TGA and DSC) and X-ray powder diffraction. Thermal processing of 1 resulted in the formation of mixed-metal oxide phases, Ba(4)Nb(2)O(9) and Ba(5)Nb(4)O(15). Three stable polymorphs of Ba(4)Nb(2)O(9) were isolated: the known, hexagonal α- and orthorhombic γ-Ba(4)Nb(2)O(9), and another one, not previously reported, hexagonal δ-Ba(4)Nb(2)O(9) polymorph. The new, δ-Ba(4)Nb(2)O(9) polymorph has the 6H-perovskite structure (space group P6(3)/m), in which the Nb(2)O(9)(8-) face-sharing octahedral dimers are interconnected via corners to the regular BaO(6)(10-) octahedra. Formation of the mixed-metal oxides takes place at different temperatures: the Ba(5)Nb(4)O(15) oxide occurred at ∼700 °C, as the major crystalline oxide phase; by heating the sample up to 1135 °C, the α-Ba(4)Nb(2)O(9) form was obtained, whereas the heating at 1175 °C caused the crystallization of two polymorphs, γ-Ba(4)Nb(2)O(9) and δ-Ba(4)Nb(2)O(9). Special focus was set on the electrical properties of the prepared mixed Ba(II)-Nb(V) oxides obtained by this molecular pathway in a single-step preparation.

Supramolecular motifs and solvatomorphism within the compounds [M(bpy)3]2[NbO(C2O4)(3)]Cl.nH2O (M = Fe2+, Co2+, Ni2+, Cu2+ and Zn2+; n = 11, 12). Syntheses, structures and magnetic properties.

Solvatomorphism has been found between two series of complexes of the composition [M(bpy)3]2[NbO(C2O4)3]Cl.nH2O [M = Fe2+ (1, 2), Co2+ (3, 4), Ni2+ (5, 6), Cu2+ (7) and Zn2+ (8, 9); bpy = 2,2'-bipyridine)], crystallizing in the monoclinic space group P2 1/c [3, 5, 8 (n = 11)] or in the orthorhombic space group P21 21 21 [2, 4, 6, 7 (n = 12)]. All the structures contain two symmetry independent [M(bpy)3]2+ cations, one [NbO(C2O4)3]3- anion, one Cl(-) anion, and crystal water molecules. The cations possess a trigonally distorted octahedral geometry, with an additional tetragonal distortion in 7. Analysis of crystal packing reveals a specific type of supramolecular contact comprising four bipyridine ligands from two neighbouring [M(bpy)3]2+ cations--quadruple aryl embrace (QAE) contact. The contact is realized by the alignment of two molecular two-fold rotation axes, preserving the parallel orientation of the molecular three-fold rotation axes. The resulting two-dimensional honeycomb lattices of [M(bpy)3]2+ cations are placed between the hydrogen bonding layers made of [NbO(C2O4)3]3- and Cl(-) anions and the majority of the crystal water molecules. The temperature-dependent magnetic susceptibility measurements (1.8-300 K) show a significant orbital angular momentum contribution for 3 and 4 (high-spin Co2+), the influence of zero-field splitting for 5 and 6(Ni2+) and a substantially paramagnetic Curie behaviour for the Cu2+ compound (7).

Hexaaquadodeca-mu-bromo-octahedro-hexatantalum bromide chloride octahydrate.

The title compound, [Ta(6)Br(12)(H(2)O)(6)](Br(0.4)Cl(1.6)) x 8H(2)O, crystallizes in space group P 1 macro. The structure contains two crystallographically independent [Ta(6)Br(12)(H(2)O)(6)](2+) cluster cations forming distinct layers parallel to the ab plane. The compound is isoconfigurational with the double salts [Ta(6)Br(12)(H(2)O)(6)]X(2) x trans-[Ta(6)Br(12)(OH)(4)(H(2)O)(2)] x 18H(2)O (X = Cl, Br).

Bis(tetramethylammonium) hexaaquadodeca-mu-bromo-octahedro-hexatantalum tetrabromide dihydrate.

The novel title compound, [(CH(3))(4)N](2)[Ta(6)Br(12)(H(2)O)(6)]Br(4) x 2H(2)O, with a [Ta(6)Br(12)]2+ cluster unit, has been prepared and structurally characterized. The compound crystallizes in space group C2/c, with a twofold axis passing through the cluster and the centre of symmetry located between the clusters. The nearest neighbouring cluster units are aligned along the crystallographic c axis, forming a one-dimensional chain pattern.