ChemInform Abstract: Crystal Structure of Magnesium Selenate Heptahydrate,MgSeO4·7H2O,from Neutron Time‐of‐Flight Data.

Crystals of MgSeO₄·7H₂O are obtained from an aqueous solution of MgO and H₂SeO₄ at 340 K, with a pH change from 0.11 to 8.8 indicating the completion of the reaction.     

ChemInform Abstract: Anosovite‐Type V3O5: A New Binary Oxide of Vanadium.

The new anosovite‐type polymorph of the title compound is synthesized by reaction of either V₂F₆·4H₂O or a mixture of 60 wt.% VF₂·4H₂O and 40 wt.% VF₃·3H₂O with a flowing water‐saturated gaseous mixture of 15—20 vol% H₂ in argon (588 K, 14—18 h).     

ChemInform Abstract: μ‐Oxido‐bis(pentammine Iron(III))‐chloride‐ammonia(1/8), [Fe2(μ—O)(NH3)10] Cl4·8NH3.

The title compound is synthesized by reaction of FeCl₃·6H₂O with liquid NH₃ and characterized by single crystal XRD.     

ChemInform Abstract: Rational Syntheses and Structural Characterization of Sulfur‐Rich Phosphorus Polysulfides: α‐P2S7 and β‐P2S7.

The polysulfides α‐ and β‐P₂S₇ are synthesized by heating stoichiometric mixtures of P₄S₃ and sulfur in the presence of catalytic amounts of anhydrous FeCl₃ as mineralizer (evacuated silica tube, 250 °C, 10 d).     

ChemInform Abstract: A Structural Investigation of Hydrous and Anhydrous Rare‐Earth Phosphates.

Rhabdophane‐type LnPO₄·nH₂O (Ln: La, Nd, Sm, Gd, Dy) and xenotime‐type Ln′PO₄·nH₂O (Ln′: Y, Yb) are prepared by a precipitation‐based method and characterized by powder XRD and XANES.     

ChemInform Abstract: Magnesium Perchlorate Anhydrate,Mg(ClO4)2, from Laboratory X‐Ray Powder Data.

The title compound is prepared by dehydration of Mg(ClO₄)₂·6H₂O (silica tube, continuous vacuum, 523 K, 2 h) and characterized by powder XRD.     

ChemInform Abstract: Na2MoO2‐δF4+δ — A Perovskite with a Unique Combination of Atomic Orderings and Octahedral Tilts.

The title compound (δ ≈ 0.08) is hydrothermally synthesized from a mixture of NaF, MoO₃, MoO₂, guanidinium carbonate, and HF in H₂O (autoclave, 160 °C, 3 d).     

ChemInform Abstract: Crystal Structure and Spectroscopic Studies of LiNH4(H2PO4)2 — A New Solid Acid in the LiH2PO4—NH4H2PO4 System.

LiNH₄(H₂PO₄)₂ is prepared from an equimolar aqueous mixture of NH₄H₂PO₄ and LiH₂PO₄ by slow evaporation at 25 °C.     

ChemInform Abstract: A New Naturally‐Occurring Nanoporous Copper Sheet‐Silicate with 6482 Cages Related to Synthetic “CuSH” Phases.

The structure of a new naturally‐occurring nanoporous copper silicate of formula Na₂CaCu₂Si₈O₂₀ ·H₂O is reported and its relations to synthetic nanoporous, so‐called CuSH phases is discussed.     

ChemInform Abstract: From 1∞ [(UO2)2O(MoO4)4]6‐ to 1∞ [(UO2)2(MoO4)3(MoO5)] 6‐ Infinite Chains in A6U2Mo4O21 (A: Na,K, Rb,Cs) Compounds: Synthesis and Crystal Structure of Cs6 [(UO2)2(MoO4)3(MoO5)] .

Single crystals of the title compound are obtained from a melt of U₃O₈, MoO₃, and excess Cs₂CO₃ (Pt crucible, 950 °C, 12 h, cooling rate 5 °C/h).     

ChemInform Abstract: Structural and Electrochemical Study od a New Crystalline Hydrate Iron(III) Phosphate FePO4·H2O Obtained from LiFePO4(OH) by Ion Exchange.

FePO₄·H₂O is prepared by Li⁺/H⁺ exchange from an aqueous HNO₃ suspension of LiFePO₄(OH) at about 60 °C.     

ChemInform Abstract: Strontium Magnesium Phosphate,Sr2+xMg3‐xP4O15 (x ≈ 0.36), from Laboratory X‐Ray Powder Data.

The title compound is synthesized by solid state reaction of SrCO₃, MgO, and (NH₄)₂HPO₄ (air, 1303 K, 4 h and 1323 K, 4 h, 90% yield) and its structure is determined by powder XRD.     

ChemInform Abstract: Crystal Structure of Potassium Sodium Heptahydrogen Hexamolybdocobaltate(III) Octahydrate: An Extra‐Protonated B‐Series Anderson‐Type Heteropolyoxidometalate.

KNa[Co^III(OH)₇{Mo₆O₁₇}] ·8H₂O is obtained by ion‐exchange from a solution of K₃ [Co(μ₃‐OH)₆Mo₆O₁₈] ·7H₂O at ≈pH 1.4 using Amberlite IR120 ion exchange resin followed by concentrating the solution in a hot water bath.     

Mass spectrometry of graphite intercalation compounds of binary fluorides of xenon,xenon oxide tetrafluoride and arsenic pentafluoride

Thermal decomposition of the intercalates of XeF₆, XeF₄, XeOF₄ and AsF₅ in graphite has been studied using a molecular beam source mass spectrometer. The product of the hydrolysis of the intercalate of XeF₆ has also been examined. The species liberated at low temperatures (T < 150°C) may be either the ones originally intercalated (XeOF₄, AsF₅) or the next lower oxidation state (XeF₄ from XeF₆, and XeF₂ from XeF₄. At higher temperatures (200-400°C) the intercalated XeF₄, XeF₂ or XeF₄ attack the graphite lattice, and evolve large quantities of xenon, and subsequently fluorocarbons and/or carbonyl fluoride. In contrast, the intercalate of AsF₅ evolves AsF₅ as the dominant gas over most of the temperature range, with a much lower degree of fluorination of the graphite lattice. The hydrolysis product of the XeF₆ intercalate was similar to the intercalate of XeF₄, but the evidence indicates that the hydrolysis proceeded well beyond XeOF₄. The extent of attack upon the graphite lattice correlates well with the oxidizing or fluorinating ability of the intercalated compound.     

A Raman spectroscopic study of the XeOF4/XeF2 system and the X-ray crystal structure of α-XeOF4·XeF2

The mixed oxidation state complexes, α-XeOF₄·XeF₂ and β-XeOF₄·XeF₂, result from the interaction of XeF₂ with excess XeOF₄. The X-ray crystal structure of the more stable α-phase shows that the XeF₂ molecules are symmetrically coordinated through their fluorine ligands to the Xe(VI) atoms of the XeOF₄ molecules which are, in turn, coordinated to four XeF₂ molecules. The high-temperature phase, β-XeOF₄·XeF₂, was identified by low-temperature Raman spectroscopy in admixture with α-XeOF₄·XeF₂; however, the instability of the β-phase precluded its isolation and characterization by single-crystal X-ray diffraction. The Raman spectrum of β-XeOF₄·XeF₂ indicates that the oxygen atom of XeOF₄ interacts less strongly with the XeF₂ molecules in its crystal lattice than in α-XeOF₄·XeF₂. The ¹⁹F and ¹²⁹Xe NMR spectra of XeF₂ in liquid XeOF₄ at −35 °C indicate that any intermolecular interactions that exist between XeF₂ and XeOF₄ are weak and labile on the NMR time scale. Quantum-chemical calculations at the B3LYP and PBE1PBE levels of theory were used to obtain the gas-phase geometries and vibrational frequencies as well as the NBO bond orders, valencies, and NPA charges for the model compounds, 2XeOF₄·XeF₂, and XeOF₄·4XeF₂, which provide approximations of the local XeF₂ and XeOF₄ environments in the crystal structure of α-XeOF₄·XeF₂. The assignments of the Raman spectra (−150 °C) of α- and β-XeOF₄·XeF₂ have been aided by the calculated vibrational frequencies for the model compounds. The fluorine bridge interactions in α- and β-XeOF₄·XeF₂ are among the weakest for known compounds in which XeF₂ functions as a ligand, whereas such fluorine bridge interactions are considerably weaker in β-XeOF₄·XeF₂.     

Group 6 Oxyfluoro-Anion Salts of [XeF5]+ and [Xe2F11]+: Syntheses and Structures of [XeF5][M2O2F9] (M=Mo,W), [Xe2F11][M′OF5] (M′=Cr,Mo, W), [XeF5][HF2]⋅CrOF4, and [XeF5][WOF5]⋅XeOF4

The reactions of the fluoride-ion donor, XeF₆, with the fluoride-ion acceptors, M′OF₄ (M′=Cr, Mo, W), yield [XeF₅]⁺ and [Xe₂F₁₁]⁺ salts of [M′OF₅]⁻ and [M₂O₂F₉]⁻ (M=Mo, W). Xenon hexafluoride and MOF₄ react in anhydrous hydrogen fluoride (aHF) to give equilibrium mixtures of [Xe₂F₁₁]⁺, [XeF₅]⁺, [(HF)_nF]⁻, [MOF₅]⁻, and [M₂O₂F₉]⁻ from which the title salts were crystallized. The [XeF₅][CrOF₅] and [Xe₂F₁₁][CrOF₅] salts could not be formed from mixtures of CrOF₄ and XeF₆ in aHF at low temperature (LT) owing to the low fluoride-ion affinity of CrOF₄, but yielded [XeF₅][HF₂]⋅CrOF₄ instead. In contrast, MoOF₄ and WOF₄ are sufficiently Lewis acidic to abstract F⁻ ion from [(HF)_nF]⁻ in aHF to give the [MOF₅]⁻ and [M₂O₂F₉]⁻ salts of [XeF₅]⁺ and [Xe₂F₁₁]⁺. To circumvent [(HF)_nF]⁻ formation, [Xe₂F₁₁][CrOF₅] was synthesized at LT in CF₂ClCF₂Cl solvent. The salts were characterized by LT Raman spectroscopy and LT single-crystal X-ray diffraction, which provided the first X-ray crystal structure of the [CrOF₅]⁻ anion and high-precision geometric parameters for [MOF₅]⁻ and [M₂O₂F₉]⁻. Hydrolysis of [Xe₂F₁₁][WOF₅] by water contaminant in HF solvent yielded [XeF₅][WOF₅]⋅XeOF₄. Quantum-chemical calculations were carried out for M′OF₄, [M′OF₅]⁻, [M′₂O₂F₉]⁻, {[Xe₂F₁₁][CrOF₅]}₂, [Xe₂F₁₁][MOF₅], and {[XeF₅][M₂O₂F₉]}₂ to obtain their gas-phase geometries and vibrational frequencies to aid in their vibrational mode assignments and to assess chemical bonding.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

ChemInform Abstract: Synthesis and Crystal Growth of Microcrystals of the Cubic and New Orthorhombic Polymorphs of (NH4)2SnCl6.

Single crystals of (NH₄)₂SnCl₆ are obtained by thermal decomposition of SnCl₄·5NH₃ in the gas phase under a stream of gaseous NH₃ (quartz tube, 298 °C, 6 h).     

ChemInform Abstract: 2Mg(OH)2·MgCl2·2H2O and 2Mg(OH)2·MgCl2·4H2O,Two High Temperature Phases of the Magnesia Cement System.

The title materials exist as stable phases in the MgO—MgCl₂—H₂O system at 120 °C.     

ChemInform Abstract: Polymorphism of New Rubidium Magnesium Monophosphate.

RbMgPO₄ is synthesized by solid state reaction of stoichiometric mixtures of Rb₂CO₃, 4MgCO₃·Mg(OH)₂·5H₂O, and (NH₄)₂HPO₄ (900 °C, 12 h).