[R-C7H16N2][V2Te2O10] and [S-C7H16N2][V2Te2O10]; new polar templated vanadium tellurite enantiomers

New polar vanadium tellurite enantiomers have been synthesized under mild hydrothermal conditions through the use of sodium metavanadate, sodium tellurite and enantiomerically pure sources of either R-3-aminioquinuclidine or S-3-aminioquinuclidine. [R-C₇H₁₆N₂][V₂Te₂O₁₀] and [S-C₇H₁₆N₂][V₂Te₂O₁₀] contain [V₂Te₂O₁₀]_n²ⁿ⁻ layers constructed from [(VO₂)₂O(TeO₄)₂] monomers. Steric effects associated with the hydrogen-bonding network between the [V₂Te₂O₁₀]_n²ⁿ⁻ layers and [C₇H₁₆N₂]²⁺ result in polar structures and crystallization in the space group P2₁ (no. 4). Electron localization functions were calculated to visualize the tellurite stereoactive lone pairs. Both iterative and non-iterative Hirshfeld techniques were evaluated as means to determine atomic partial charges, with iterative Hirshfeld charges more accurately representing charge distributions in the reported enantiomers. These charges were used to calculate both component and net dipole moments. [R-C₇H₁₆N₂][V₂Te₂O₁₀] and [S-C₇H₁₆N₂][V₂Te₂O₁₀] exhibit dipole moments of 17.37 and 16.62D, respectively. [R-C₇H₁₆N₂][V₂Te₂O₁₀] and [S-C₇H₁₆N₂][V₂Te₂O₁₀] both display type 1 phase-matching capabilities and exhibit second harmonic generation activities of ∼50×α-SiO₂.     

La4(Si5.2Ge2.8O18)(TeO3)4 and La2(Si6O13)(TeO3)2: Intergrowth of the lanthanum(III) tellurite layer with the XO4 (X=Si/Ge) tetrahedral layer

Two novel lanthanum(III) silicate tellurites, namely, La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ and La₂(Si₆O₁₃)(TeO₃)₂, have been synthesized by the solid state reactions and their structures determined by single crystal X-ray diffraction. The structure of La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ features a three-dimensional (3D) network composed of the [(Ge_2.82Si_5.18)O₁₈]⁴⁻ tetrahedral layers and the [La₄(TeO₃)₄]⁴⁺ layers that alternate along the b-axis. The germanate-silicate layer consists of corner-sharing XO₄ (X=Si/Ge) tetrahedra, forming four- and six-member rings. The structure of La₂(Si₆O₁₃)(TeO₃)₂ is a 3D network composed of the [Si₆O₁₃]²⁻ double layers and the [La₂(TeO₃)₂]²⁺ layers that alternate along the a-axis. The [Si₆O₁₃]²⁻ double layer is built by corner-sharing silicate tetrahedra, forming four-, five- and eight-member rings. The TeO₃²⁻ anions in both compounds are only involved in the coordination with La³⁺ ions to form a lanthanum(III) tellurite layer. La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ is a wide band-gap semiconductor.     

Hydrothermal Syntheses, Structures, and Properties of Two New Potassium Vanadium Phosphates: K3(VO) (V2O3) (PO4)2(HPO4) and K3 (VO) (HV2O3) (PO4)2(HPO4)

Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K₃(VO)(V₂O₃) (PO₄)₂(HPO₄) and K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO]_n chains connected through phosphate groups to a [V₂O₃] moiety. Magnetic susceptibility experiments indicate that in the case of the di-hydrogen compound, there are no significant magnetic interactions between the three independent vanadium (IV) centers. Crystal data: for K₃(VO)(V₂O₃)(PO₄)₂ (HPO₄), M_r = 620.02, orthorhombic space group Pnma (No. 62), a = 7.023(4) Å, b = 13.309(7) Å, c = 14.294(7) Å, V = 1336(2) ų, Z = 4, R = 5.02%, and R_w = 5.24% for 1238 observed reflections [I > 3σ(I)]; for K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), M_r = 621.04, orthorhombic space group Pnma (No. 62), a = 6.975(3) Å, b = 13.559(7) Å, c = 14.130(7) Å, V = 1336(1) ų, Z = 4, R = 6.02%, and R_w = 6.34% for 1465 observed reflections [I > 3σ(I)].     

Phase diagram and infrared-spectral investigation of the 2TeO2 · V2O5-Na2O · V2O5 · 2TeO2 system

The phase diagram of the 2TeO₂ · V₂O₅-Na₂O · V₂O₅ · 2TeO₂ system is studied by X-ray diffraction, ir spectroscopy, and DTA. A new compound with a composition of Na₂O · 3V₂O₅ · 6TeO₂ is established. The ir spectra of the alkaline trivanadates are interpreted. They are considered as structural analogs of the new phase. As a result of this comparison, the postulate is made that the main structural units in the Na₂O · 3V₂O₅ · 6TeO₂ compound are V₂O₈ groups, while tellurium is present both in the TeO₃ and TeO₄ groups. Contrary to the crystal phases, in glasses the transition from VO₅ toward VO₄ does not proceed through the formation of new structural units of vanadium; but rather a gradual transition of the structure is observed with a change in the composition from 2TeO₂ · V₂O₅ to Na₂O · V₂O₅ · 2TeO₂.     

A layered vanadium arsenate network decorated with the directly coordinated organonitrogen ligands: [V4O7(HAsO4)2(o-phen)2] (o-phen=o-phenanthroline)

A novel layered vanadium arsenate [V₄O₇(HAsO₄)₂(o-phen)₂] 1 (o-phen=o-phenanthroline) was synthesized by the hydrothermal reaction of V₂O₅, ZnCl₂, Na₂HAsO₄·7H₂O, o-phenanthroline (o-phen) and water. Its structure was determined by elemental analyses, ESR spectrum, XPS spectrum, TG analysis, IR spectrum and the single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic system, space group P2/c, a=10.122(2) Å, b=9.867(2) Å, c=15.367(3) Å, β=102.83(3)°, V=1496.4(5) Å³, Z=1, λ(MoKα)=0.71073 Å, (R(F)=0.0397 for 3422 reflections). Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 2.06°<θ<27.48°. The title compound contains an unusual two-dimensional (2D) As-V-O layer with four-, six- and eight-membered rings. The chelating o-phen ligands project perpendicularly above and below the undulating layer. 1 represents the first example of 2D inorganic vanadium arsenate backbone grafted with the directly coordinated organic ligands. Furthermore, the 3D supermolecular architecture is formed by π-π stacking interactions of the o-phen groups between adjacent layers.     

Syntheses and crystal structures of the first organically templated metal tellurites

The first organically templated vanadium tellurites, [H₂en][(VO₂)(TeO₃)]₂·H₂O (1, en=ethylenediamine) and [H₂pip][(VO₂)(TeO₃)]₂ (2, pip=piperazine) have been synthesized by hydrothermal reactions and structurally characterized. Both compounds feature a [(VO₂)(TeO₃)]⁻ anionic layer containing V₂Te₂ four-member rings and V₄Te₄ eight member rings. The vanadium (V) atom is five coordinated by three tellurite oxygens and two terminal oxygen atoms in a distorted trigonal bipyramidal geometry. The interconnection of the VO₅ polyhedra by bridging tellurite groups leads to a 2D corrugated anionic inorganic layer. The doubly protonated template cations and the lattice water molecules in 1 are located at the interlayer space and are involved in hydrogen bonding. The doubly protonated template cation in 2 is not involved in hydrogen bonding with the anionic inorganic layer.     

Hydrothermal Synthesis of a New Vanadium Tellurate(VI) with a Novel Chain Structure: (NH4)4{(VO2)2[Te2O8(OH)2]}·2H2O

A new ammonium vanadium tellurate, (NH₄)₄{(VO₂)₂[Te₂O₈(OH)₂]}·2H₂O ( 1 ) was hydrothermally synthesized and characterized by elemental analyses, IR spectrum, TG analysis, and single crystal X–ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2₁/n, a = 7.3843(15) Å, b = 17.111(3) Å, c = 7.3916(15) Å, β = 118.88(3)°, V = 817.9(3) ų, Z = 2, R1 (I>2σ(I)) = 0.0235, wR2 (all data) = 0.0462. The structure of 1 consists of infinite anionic chains, {(VO₂)₂[Te₂O₈(OH)₂]}^4? which contain octahedral VO₆ and TeO₅OH units. Each octahedral VO₆ and TeO₅OH unit is connected by sharing an edge to form V₂O₁₀ and Te₂O₈(OH)₂ binuclear units. The V₂O₁₀ and Te₂O₈(OH)₂ binuclear units are alternatively connected to one another, creating complete infinite {(VO₂)₂[Te₂O₈(OH)₂]}^4? chains along the c direction. The anionic chains are separated by ammonium cations and water molecules that link the chains through a network of hydrogen bonds. In addition, the structure contains an extended network of O–H·····O hydrogen bonds between the chains.     

Hydrothermal synthesis and characterization of the tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate: {PW4W5V3O40(VO)3[Cu(en)2]}

A novel polyoxometalate [Cu(phen)₂]₃{PW₄^VIW₅^VV₃^IVO₄₀(V^IVO)₃[Cu(en)₂]}4H₂O 1 (en=ethylenediamine, phen=1,10-phenanthroline) has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TG, EPR and single-crystal X-ray diffraction analysis. The crystal structure analysis shows that compound 1 contains a novel highly reduced tri-capped and mono-supported pseudo-Keggin-type heteropolyanion, {PW₄^VIW₅^VV₃^IVO₄₀(V^IVO)₃[Cu(en)₂]}⁶⁻, three [Cu(phen)₂]²⁺ cations and four lattice water molecules. They are further linked to form three-dimensional supramolecular networks through extensive hydrogen bonding and π–π stacking interactions. Interestingly, the water dimer and terminal oxygen of the cluster polyanion constitute a beautiful supramolecular helix chain. The heteropolyanion is the first example of tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate and the pH value is crucial for obtaining compound 1 in synthetic procedure.     

Synthesis, crystal and band structures, and optical properties of a new lanthanide-alkaline earth tellurium(IV) oxide: La2Ba(Te3O8)(TeO3)2

A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La₂Ba(Te₃O₈)(TeO₃)₂, has been prepared by the solid-state reaction and structurally characterized. The compound crystallizes in monoclinic space group C2/c with a=19.119(3), b=5.9923(5), c=13.2970(19) Å, β=107.646(8)°, V=1451.7(3) Å³ and Z=4. La₂Ba(Te₃O₈)(TeO₃)₂ features a 3D network structure in which the cationic [La₂Ba(TeO₃)₂]⁴⁺ layers are cross-linked by Te₃O₈⁴⁻ anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La₂Ba(Te₃O₈)(TeO₃)₂ is a wide band-gap semiconductor.     

Magnetic and catalytic properties of the 2D copper(II) functionalized VPO hybrid system [{Cu(bpy)}2(VO)3(PO4)2(HPO4)2]·2H2O

The hybrid 2D compound [{Cu(bpy)}₂(VO)₃(PO₄)₂(HPO₄)₂]·2H₂O (1), has been investigated due to its interesting magnetic and catalytic properties. Compound (1) acts as an efficient catalyst in the epoxidation of cyclohexene and styrene. The chemoselectivity towards the epoxidation of cyclohexene is notoriously higher than the one observed towards styrene. The bulk antiferromagnetic behaviour of [{Cu(bpy)}₂(VO)₃(PO₄)₂(HPO₄)₂]·2H₂O (1) can be well described with a pentanuclear model, using five J values. Both antiferromagnetic and ferromagnetic interactions mediated by phosphate bridges are found to be present in this hybrid copper(II)–vanadium(IV) material.     

Synthesis and structure determination of a novel lithium copper vanadate LiCu2VO4(OH)2

A novel lithium copper vanadate LiCu₂VO₄(OH)₂ (I) and Volborthite Cu₃V₂O₇(OH)₂ are two phases obtained at 170 °C by hydrothermal synthesis during the study of the CuO; V₂O₅; Li₂O; H₂O system. Compound (I) crystallizes in the orthorhombic system, with the space group P2₁2₁2₁ (No. 19) and with the unit-cell parameters a=9.6086(2) Å, b=8.4482(2) Å, c=5.8938(1) Å. The structure was determined from powder by an “ab initio” method using the EXPO software and refined with GSAS, a Rietveld refinement package. Wave-like layers of rutile-type copper chains sharing vertex with the neighbor chains, are linked into a three-dimensional framework by rows of alternating tetrahedra of vanadium and trigonal bipyramids of lithium which share edges and vertices with the copper octahedra.     

Synthesis and Properties of the Mixed Hydrated Oxides V2?yWyO5 + δ < eqid2 > nH2O

Compounds of the general formula V_{2 − y}W_yO_{5 + δ} < eqid3 > nH₂O (0 < y ≤ 0.25) with the layered structure of polyvanadic acid V₂O₅ < eqid4 > nH₂O (H₂V₁₂O_{31 − δ} < eqid5 > nH₂O) have been prepared from peroxide solutions using the sol–gel process. The samples contain up to 5–8 wt% vanadium (IV). The water content changes within the range of 0.7 ≤ n ≤ 1.5 in depending on tungsten concentration. The V_{2 − y}W_yO_{5 + δ} < eqid6 > nH₂O (y ≤ 0.125) form the thin films described an interlayer distance of 11.60 ± 0.05 Å. The thermal properties, IR, and X-ray photoelectron spectra of the compounds synthesized have been studied. The thermal stability of the phases increases with the rising of tungsten content. The dehydration finishes with the forming solid solution V_2−yW_yO₅ and WO₃. The electrical conductivity of V_2−yW_yO_{5 + δ} < eqid7 > nH₂O (0 < y ≤ 0.25) powders was measured between 293 and 473 K at a relative humidity of 12%. The activation energy of conduction is independent upon the W content and equals 0.22–0.24 eV. Partial substitution of vanadium for tungsten was found to reduce the conductivity of the phases. The conductivity of the films increases with the increasing of relative air humidity and is governed by proton diffusion across the V-O-W layers.     

Novel M(II)–Hg(II) coordination polymers generated from metal-containing building blocks M(2-pyrazinecarboxylate)2 · (H2O)2 (M=Cu, Ni, Co) and HgCl2

A new class of M(II)–Hg(II) (M=Cu(II), Co(II), Ni(II)) mixed-metal coordination polymers, Cu(2-pyrazinecarboxylate)₂HgCl₂ (4), [Co(2-pyrazinecarboxylate)₂(HgCl₂)₂] · 0.61H₂O (5) and [Ni(2-pyrazinecarboxylate)₂(HgCl₂)₂] · 0.77H₂O (6), have been prepared by self assembly of metal-containing building blocks, M(2-pyrazinecarboxylate)₂ · (H₂O)₂(M=Cu(II), Co(II), Ni(II)), with HgCl₂. Compounds 4–6 were characterized fully by IR, elemental analysis and single crystal X-ray diffraction. Compound 4 crystallized in the monoclinic space group C2/c, with a=17.916(5) Å, b=7.223(2) Å, c=13.335(4) Å, β=128.726(3)°, V=1346.2(6) ų, Z=4. It contains alternating Hg(II) and Cu(II) metal centers that are cross-linked by 2-pyrazinecarboxylate spacers and chlorine co-ligands to generate a unique three-dimensional Hg(II)–Cu(II) mixed metal framework. Compound 5 crystallized in the triclinic space group P , with a=6.3879(7) Å, b=6.6626(8) Å, c=13.2286(15) Å, α=96.339(2)°, β=91.590(2)°, γ=113.462(2)°, V=511.71(10) ų, Z=1. Compound 6 also crystallized in the triclinic space group P , with a=6.3543(8) Å, b=6.6194(8) Å, c=13.2801(16) Å, α=96.449(2)°, β=92.263(2)°, γ=113.541(2)°, V=506.67(11) ų, Z=1. Compounds 5 and 6 are isostructural and in the solid state the Hg(II)M(II)Hg(II) units are connected by Hg₂Cl₂ linkages to produce a novel M(II)–Hg(II) (M=Co(II), Ni(II)) zigzag mixed-metal chain, in which a new type of M–M′–M′–M array was observed. The metal containing building blocks, M(2-pyrazinecarboxylate)₂ · (H₂O)₂ (M=Cu(II), Co(II), Ni(II)), exhibit different connectivities to HgCl₂ depending on the metal cation contained within them.     

Hydrothermal Synthesis and Characterization of (H3N(CH2)4NH3)[V6O14]

A new layered vanadium oxide [H₃N(CH₂)₄NH₃](V₆O₁₄) was synthesized hydrothermally under autogenous pressure at 180°C for 48 h from a mixture of H₂N(CH₂)₄NH₂ and V₂O₅ in aqueous solution. Its structure was determined from single-crystal X-ray diffraction at room temperature with final R=0.0774 and R_w=0.0893. It crystallizes in the monoclinic system (space group P2₁/n with a=9.74(2) Å, b=6.776(5) Å, c=12.60(2) Å, β=96.1(1)°, V=827(2) ų and Z=2). This compound contains mixed-valence V⁵⁺/V⁴⁺ vanadium oxide layers built from [V^VO₄] tetrahedra and pairs of edge-sharing [V^IVO₅] square pyramids with protonated organic amines occupying the interlayer space.     

Synthesis and Crystal Structure of Cs(VO2)3(TeO3)2, a New Layered Cesium Vanadium(V) Tellurite

Synthetic Cs(VO₂)₃(TeO₃)₂ is built up from infinite sheets of distorted octahedral V^VO₆ groups, sharing vertices. These octahedral layers are “capped” by Te atoms (as parts of pyramidal [Te^IVO₃]^2– groups) on both faces of each V/O sheet, with inter‐layer, 12‐coordinate, Cs⁺ cations providing charge compensation. Cs(VO₂)₃(TeO₃)₂ is isostructural with M(VO₂)₃(SeO₃)₂ (M = NH₄, K). Crystal data: Cs(VO₂)₃(TeO₃)₂, M_r = 732.93, hexagonal, space group P6₃ (No. 173), a = 7.2351(9) Å, c = 11.584(2) Å, V = 525.1(2) ų, Z = 2, R(F) = 0.030, wR(F ²) = 0.063.     

A novel organically templated three-dimensional open framework vanadium tellurite: (NH3CH2CH2NH3)2V2Te6O18

A novel organically templated vanadium tellurite (NH₃CH₂CH₂NH₃)₂V₂Te₆O₁₈ (1) has been hydrothermally synthesized and characterized by elemental analyses, IR, thermal stability analysis, magnetic susceptibilities and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2₁/n, , , , β=94.789(4)°, , Z=2, R₁[I>2σ(I)]=0.0187, wR₂[I>2σ(I)]=0.0482. Compound 1 exhibits a novel three-dimensional (3D) vanadium tellurite anion framework composed of vanadium, tellurium, and oxygen atoms through covalent bonds, with the [NH₃CH₂CH₂NH₃]²⁺ cations residing in the channels.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Hydrothermal syntheses and structures of the uranyl tellurates AgUO2(HTeO5) and Pb2UO2(TeO6)

Two uranyl tellurates, AgUO₂(HTeO₅) (1) and Pb₂UO₂(TeO₆) (2), were synthesized under hydrothermal conditions and were structurally, chemically, and spectroscopically characterized. 1 crystallizes in space group Pbca, a=7.085(2) Å, b=11.986(3) Å, c=13.913(4) Å, V=1181.5(5) Å³, Z=8; 2 is in P2(1)/c, a=5.742(1) Å, b=7.789(2) Å, c=7.928(2) Å, V=90.703(2) Å³, and Z=2. These are the first structures reported for uranyl compounds containing tellurate. The U⁶⁺ cations are present as (UO₂)²⁺ uranyl ions that are coordinated by O atoms to give pentagonal and square bipyramids in compounds 1 and 2, respectively. The structural unit in 1 is a sheet consisting of chains of edge-sharing uranyl pentagonal bipyramids that are one bipyramid wide, linked through the dimers of TeO₆ octahedra. In 2, uranyl square bipyramids share each of their equatorial vertices with different TeO₆ octahedra, giving a sheet with the autunite-type topology. Sheets in 1 and 2 are connected through the low-valence cations that are located in the interlayer region. The structures of 1 and 2 are compared to those of uranyl compounds containing octahedrally coordinated cations.     

Influence of the size of aromatic chelate ligands on the one-dimensional chains of copper(II) dicarboxylate coordination polymers

To investigate the influence of the size of aromatic chelate ligands on the frameworks of metal dicarboxylate polymers, two one-dimensional coordination compounds [Cu(BDC)(TATP)(H₂O)] _n (I) and [Cu(BDC)(DPPZ)] _n (II), (BDC = 1.4-benzenedicarboxylate, TATP = 1,4,8,9-tetranitrogentrisphene, DPPZ = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized under similar conditions and structurally characterized by X-ray crystallography. Compounds I and II have the similar zigzag chain structure, but the substitution of TATP with DPPZ results in the difference of the degree of bending of the chain, indicating that the sizes of the rigid aromatic chelate ligands have important effect on the structures of their complexes.     

IR-Spektralanalyse von Gl?sern des Systems TeO2?V2O5

Studies of glasses and their crystalline products in the TeO₂–V₂O₅ system were made in the 1400–400 cm^–1 range. A continuous shift of the V=O-band from 1020 cm^–1 to 940 cm^–1 was found in the glasses with decreasing concentration of V₂O₅, as well as a sharp decrease in the intensity at 830 cm^–1. On the basis of the results obtained, it is concluded that with increasing TeO₂ content, the structure of the glasses is changed, caused by the breaking of the V–O–V bonds and the formation of Te–O–Te bridges.The IR-spectrum of the 2TeO₂·V₂O₅ compound in both crystalline and vitreous states was studied for the first time. The behaviour of the absorption bands is related to the structure of the glasses studied.