Na2Co(H2PO4)4·4H2O

In the title compound, disodium cobalt tetrakis­(dihydrogen­phosphate) tetrahydrate, the Co^II ion lies on an inversion centre and is octahedrally surrounded by two water molecules and four H₂PO₄ groups to give a cobalt complex anion of the form [Co(H₂PO₄)₄(OH₂)]^2?. The three‐dimensional framework results from hydrogen bonding between the anions. The relationship with the structures of Co(H₂PO₄)₂·2H₂O and K₂CoP₄O₁₂·5H₂O is discussed.     

A new hydrated ammonium hydroxy­borate, (NH4)2[B10O14(OH)4]·H2O

The structure of a new synthetic compound, di­ammonium tetra­hydroxy­deca­borate monohydrate, has been determined by single‐crystal X‐ray diffraction. It crystallizes in triclinic space group and all atoms occupy general sites. The title compound is composed of [B₁₀O₁₅(OH)₄]⁴⁻ ions as the fundamental building blocks, and these are linked end‐to‐end by sharing two common O atoms, thus producing infinite chains of composition [B₁₀O₁₄(OH)₄]_n^2n–. These chains are linked by hydrogen bonds, thus forming borate sheets. Water mol­ecules and ammonium ions between these sheets connect adjacent sheets via hydrogen bonds.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Two caesium vanadium hydrogenphosphates with tunnelled structures: Cs2V2O3(PO4)(HPO4) and Cs2[(VO)3(HPO4)4(H2O)]·H2O

Dicaesium divanadium trioxide phosphate hydrogenphosphate, Cs₂V₂O₃(PO₄)(HPO₄), (I), and dicaesium tris[oxidovanadate(IV)] hydrogenphosphate dihydrate, Cs₂[(VO)₃(HPO₄)₄(H₂O)]·H₂O, (II), crystallize in the monoclinic system with all atoms in general positions. The structures of the two compounds are built up from VO₆ octahedra and PO₄ tetrahedra. In (I), infinite chains of corner‐sharing VO₆ octahedra are connected to V₂O₁₀ dimers by phosphate and hydrogenphosphate groups, while in (II) three vanadium octahedra share vertices leading to V₃O₁₅(H₂O) trimers separated by hydrogenphosphate groups. Both structures show three‐dimensional frameworks with tunnels in which Cs⁺ cations are located.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Bis(ethyl­ene­di­ammonium) decaaqua­disodium decavanadate, (C2H10N2)2[Na2(H2O)10][V10O28]

In the title compound, the decavanadate anion, [V₁₀O₂₈]⁶⁻, and the bridged [Na₂(H₂O)₁₀]²⁺ dication lie across inversion centers. The charge balance is achieved by ethyl­ene­di­ammonium cations, H₃NCH₂CH₂NH₃²⁺, which are disordered. The decavanadate anions are surrounded by the [Na₂(H₂O)₁₀]²⁺ dications, thus forming layers, and the ethyl­ene­diammonium cations are located between these layers.     

(NH4)3[VO2(SO4)2(H2O)2]·1.5H2O

The title compound, tri­ammonium cis‐di­aqua‐cis‐dioxo‐trans‐disulfatovanadate 1.5‐hydrate, was obtained by oxidizing V^IV to V^V in a 2 M sulfuric acid solution of vanadyl­ sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner‐sharing to form a discrete [VO₂(SO₄)₂(OH₂)₂]^3? anion. The water mol­ecules occupy cis positions in the equatorial plane of the vanadium octahedron.     

Rb(GaPO4)2(OH)(H2O)·H2O: a hydrated rubidium gallium phosphate analogue of GaPO4·2H2O and leucophosphite

Crystals of the title hydrated rubidium gallium phosphate, rubidium aqua‐μ₃‐hydroxo‐di‐μ‐phosphato‐digallium hydrate, were synthesized hydro­thermally at 453 K under autogenous pressure. The solid crystallizes in the monoclinic system and its structure was determined from single‐crystal X‐ray diffraction analysis. It is similar to dihydrated gallium phosphate, GaPO₄·2H₂O, which is isostructural with the mineral leucophosphite. The structure is built up from a three‐dimensional anionic framework composed of corner‐linked octameric Ga₄(PO₄)₄(OH)₂(H₂O)₂ units. The Ga atom is in an octahedral coordination. Connection of the Ga₄P₄ species generates eight‐ring channels, in which are encapsulated the Rb⁺ cations and water mol­ecules.     

Preparation and Crystal Structure of Potassium Iron Hydrogen Phosphate,KFe3(HPO4)2(H2PO4)6 · 4 H2O

Single crystals of potassium iron hydrogen phosphate, KFe₃(HPO₄)₂(H₂PO₄)₆ · 4 H₂O, were prepared hydrothermally by heating a mixture of Fe₂O₃, H₃PO₄ and K₂CO₃ with a small amount of water. It crystallizes monoclinic, space group C2/c (N° 15 Int. Tab.) with Z = 4 and a = 1701(2), b = 960.4(5), c = 1750(1) pm, β = 90.88(7)°. The crystal structure was solved by using 1716 unique reflections F₀ > 4σ(F₀) with a final wR2 value of 0.126 (SHELXL-93). The main feature of the crystal structure are layers formed by PO₄-tetrahedra around the FeO₆-octahedra parallel to (001). K⁺ and H₂O molecules connect these layers. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), Charge Distribution (CHARDI) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound. The existence of hydrogen bonds is confirmed by these calculations.     

[Co(H_2O)(HPO_4)]·H_2O: The Layered Divalent Metal Monohydrogenphosphate Structure

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ChemInform Abstract: Two Caesium Vanadium Hydrogenphosphates,with Tunnelled Structures: Cs2V2O3(PO4)(HPO4) and Cs2 [(VO)3(HPO4)4(H2O)] ·H2O.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Alkalimolybdotellurate: Darstellung und Kristallstruktur von Rb6[TeMo6O24] · 10H2O und Rb6[TeMo6O24] · Te(OH)6 · 6H2O

Alkaline Molybdotellurates: Preparation and Crystal Structures of Rb₆[TeMo₆O₂₄] · 10H₂O and Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6H₂O Single crystals of Rb₆[TeMo₆O₂₄] · 10 H₂O and Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6 H₂O, respectively, were grown from aqueous solution. Rb₆[TeMo₆O₂₄] · 10 H₂O possesses the space group P1 . The lattice dimensions are a = 963.40(13), b = 972.56(12), c = 1 056.18(13) pm, α = 97.556(10), β = 113.445(9), γ = 102.075(10)°; Z = 1, 2 860 reflections, 215 parameters refined, R_g = 0.0257. The centrosymmetrical [TeMo₆O₂₄]^6? anions are stacked parallel to [010]. Rb(2) is coordinated with one exception by water molecules only. Folded chains consisting of [TeMo₆O₂₄]^6? anions and Rb(2) coordination polyhedra which are linked to pairs represent the prominent structural feature. Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6 H₂O crystallizes monoclinically in the space group C2/c with a = 1 886.4(3), b = 1 000.9(1), c = 2 126.5(3) pm, and β = 115.90(1)°; Z = 4, 3 206 reflections, 240 parameters refined, R_g = 0.0333. It is isostructural in high extent with (NH₄)₆[TeMo₆O₂₄] · Te(OH)₆ · 7 H₂O. Hydrogen bonds between Te(OH)₆ molecules and [TeMo₆O₂₄]^6? anions establish infinite strands. The [TeMo₆O₂₄]^6? anions gather around Te(OH)₆ providing channel-like voids extending parallel to [001].     

[VO(SeO3)(H2O)2]·0.5H2O

In poly[[diaquaoxido[μ₃‐trioxidoselenato(2−)]vanadium(IV)] hemihydrate], {[VO(SeO₃)(H₂O)₂]·0.5H₂O}_n, the octahedral V(H₂O)₂O₄ and pyramidal SeO₃ building units are linked by V—O—Se bonds to generate ladder‐like chains propagating along the [010] direction. A network of O—H...O hydrogen bonds helps to consolidate the structure. The O atom of the uncoordinated water molecule lies on a crystallographic twofold axis. The title compound has a similar structure to those of the reported phases [VO(OH)(H₂O)(SeO₃)]₄·2H₂O and VO(H₂O)₂(HPO₄)·2H₂O.     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Cis-/Trans-Isomerie bei Bis-(trisalkoxy)-hexavanadaten: cis-Na2[VO7(OH)6{(OCH2)3CCH2OH}2] · 8 H2O,cis-(CN3H6)3[VIVVO13{(OCH2)3CCH2OH}2] · 4,5 H2O und trans-(CN3H6)2[VO13{(OCH2)3CCH2OH}2] · H2O

Cis-/Trans-Isomerism of Bis-(trisalkoxy)-hexavanadates: cis-Na₂[V O₇(OH)₆{(OCH₂)₃CCH₂OH}₂] · 8 H₂O, cis-(CN₃H₆)₃[V^IVV O₁₃{(OCH₂)₃CCH₂OH}₂] · 4.5 H₂O and trans-(CN₃H₆)₂[V O₁₃{(OCH₂)₃CCH₂OH}₂] · H₂O Polyoxovanadates with distorted Lindquist-structure, in which six of the twelve μ₂-oxygen atoms are formally replaced by the oxygen atoms of two coordinated pentaerythritol ligands, can be prepared by a simple method in an aqueous medium. The “fully reduced”, six-fold protonated compound cis-Na₂[VO₇(OH)₆{(OCH₂)₃CCH₂OH}₂] · 8 H₂O ( 1 ), the mixed valence species cis-(CN₃H₆)₃[V^IVVO₁₃{(OCH₂)₃CCH₂OH}₂] · 4.5 H₂O ( 2 ) containing one localized V^IV centre and the “fully oxidized” compound trans-(CN₃H₆)₂[VO₁₃{(OCH₂)₃CCH₂ · OH}₂] · H₂O ( 3 ) have been synthesized and characterized by UV/VIS-, IR- and EPR-spectroscopy, by magnetic measurements, cyclic voltammetry and by a single-crystal X-ray structure analysis. The organic {(CH₂)₃CCH₂OH}³⁺-groups tend to cap the triangular faces formed by μ₂-oxygen atoms of the central approximately octahedral {V₆O₁₉}-unit. Therefore the anions of bis-(trisalkoxy)-hexavanadates can exist in a trans-form as well as in an isomeric cis-form referring to a “basic” plane of four vanadium atoms of the {V₆}-octahedron. The different relative positions of the ligands have a significant influence on the redox potentials of the compounds. For structural details see “Inhaltsübersicht”.     

Ein anionischer Oxohydroxo‐Komplex mit Bismut(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O

An Anionic Oxohydroxo Complex with Bismuth(III): Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O Colourless, plate‐like, air sensitive crystals of Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O are obtained by reaction of Bi₂O₃ or Bi(NO₃)₃ · 5H₂O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi₂O₂(OH)₆]^4— with bismuth in an ψ¹‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na₃BiO₃.