Über Fluoride des zweiwertigen Eisens: Ba2[Fe3F10]

On the Knowledge of Ba₂[Fe₃F₁₀] For the first time colourless single crystals of Ba₂Fe₃F₁₀ have been prepared by reduction of a mixture of 3 BaF₂/7 FeF₃ in a Fe-tube (reaction with the wall 750°C, 60 d). Ba₂Fe₃F₁₀ crystallizes in the monoclinic spcgr. P2₁/c with a = 788.3(1), b = 623.0(1), c = 1868.0(3) pm, β = 111.79(1)º, Z = 4. (Fourcircle diffractometer PW 1100, Fa. Philips, MoKα, 2383 of 2383 I₀(hkl), R = 8.1%, R_w = 4.1%, parameters see in the text). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Über Fluoride des zweiwertigen Eisens. Zum Aufbau von CsFeF3

Fluorides with Divalent Iron: On the Structure of CsFeF₃ By ?reaction with the wall”? according to 3 CsF + 2 FeF₃ + Fe_wall = 3 CsFeF₃ we obtained for a first time colourless single crystals of CsFeF₃. The lattice constants were redetermined with a = 616.39(6) pm, c = 1487.02(15) pm (Four circle diffractometer PW 1100, AgK$ \bar \alpha $, R = 4.33%, R_w = 2.79%). CsFeF₃ crystallizes isotypic to BaTiO₃ in the space group P6₃/m mc. Parameters see text. The Madelung Part of Lattice Energy, MAPLE, and the ?Effective Coordination Numbers”?, ECoN, via the ?Mean Fictive Ionic Radii”?, MEFIR, are calculated and discussed.     

Über Komplexe Fluoride des zweiwertigen Palladiums

On Complex Fluorides of Divalent Palladium For the first time single crystals of the new compounds RbPdPdF₅, KPdPdF₅, and K₂CsPdF₅ have been obtained. Orange brown RbPdPdF₅ crystallizes orthorhombic, space group Imma–D_2h²⁸ (No. 74) with a = 633.6(1) pm, b = 765.5.(1) pm, c = 1067.5(1) pm and Z = 4 and is isotypic with CsPdPdF₅ [1]. Structure related KPdPdF₅ (also orange brown) crystallizes orthorhombic too, but in space group Pnma–D_2h¹⁶ (No. 62) with a 614.12(9) pm, b = 748.7(1) pm, c = 1065.0(2) pm and Z = 4. K₂CsPdF₅, light yellow, crystallizes tetragonal with a = 736.3(1) pm, c = 628.0(1) pm, Z = 2, and is isotypic with Rb₂CsPdF₅ (space group P4/mbm? D_4h⁵ Nr. 127), an ordered structure variant of the Rb₃PdF₅-Type [1].     

Über Fluoride des einwertigen und des zweiwertigen Quecksilbers

On Fluorides of Univalent and Divalent Mercury For the first time Rb₂HgF₄ and Cs₂HgF₄, both colourless, have been obtained. From single crystal investigations they crystallize tetragonal in the K₂NiF₄-type of structure, space group I4/mrnm-D_4h¹⁷ (No. 139) with a = 455.6 pm, c = 1375.7 pm, Z = 2 for Rb₂HgF₄ and a = 462.5 pm, c = 1451.8 pm, Z = 2 for Cs₂HgF₄. The determination of the crystal structure of Hg₂F₂ confirmed the unit cell [1] with a = 367.00(4) pm, c = 1090.1(2) pm, Z = 2 space group I4/mrnm-D_4h¹⁷ (No. 139).     

Über neue Fluoride des Kupfers Zur Kenntnis von Cs[CuF4]

New Fluorides of Copper. On Cs[CuF₄] Due to powder diagrams, Cs[CuF₄], the first diamagnetic fluoride (χ_Mol = ?516·10^?6 cm³/Mol) of trivalent copper, with planar coordination orange-coloured, crystallizes tetragonal, K[BrF₄]-type of structure with planar [CuF₄]-units (a = 5.8488(4) Å, c = 12.043(1) Å). We obtained Cs[CuF₄] by high pressure fluorination (p_F2 = 350 bar, 400°C, 7 h) of CsCuCl₃ in autoclaves.     

Zur Kenntnis des Systems Cs/Cu/F: Über CsCuIICuIIIF6

The System Cs/Cu/F: On CsCu^IICu^IIIF₆ ?CsCuF_3,6’? is described in literature as a darkbrown powder which is supposed to crystallize in a cubic lattice (a = 882 pm, Debyeogramms). However Guinier photographs show that ?CsCuF_3,6’? is a mixture of CsCu^IICu^IIIF₆ (black, isotypic to CsNi^IINi^IIIF₆, a = 706.7 b = 727.7, c = 1032.2 pm, Z = 4) and Cs₂CuCu^IIIF₆ (auburn, pseudocubic, a = 623.4 c = 886.4 pm, Z = 2).     

Über Fluoride mit vierwertigem Kupfer: Cs2[CuF6]

Chlorides Ag₃MCl₆ have been obtained with M = Dy? Lu, Y, Sc from AgCl/MCl₃ mixtures (sealed Pyrex ampoule, 380°C, 8 d). They crystallize like Na₃GdCl₆-I with a “stuffed” LiSbF₆-type structure (R3 , Z = 3). Thermal expansion was followed for Ag₃HoCl₆ and Ag₃YCl₆ and is remarkably different from that of Na₃GdCl₆-I.     

Strukturen caesiumhaltiger Fluoride. VIII. Cs7Ni4F15 und Cs7Co4F15: Die Kristallstrukturbestimmung an den bisher caesiumreichsten Verbindungen in den zugehörigen Systemen CsF/MF2

Structures of Cesium-containing Fluorides. VIII. Cs₇Ni₄F₁₅ and Cs₇Co₄F₁₅: Crystal Structure Determination of the Hitherto Cesium-richest Compounds in the Corresponding Systems CsF/MF₂ . The only nickel-containing phase we could identify after solid state reaction 2 CsF + NiF₂ was the compound Cs₇Ni₄F₁₅. The single crystal structure determination of this monoclinic fluoride (and its cobalt analog Cs₇Co₄F₁₅) yielded a = 787.2 (788.3), b = 1089.7 (1096.6), c = 1149.5 (1164.9) pm, β = 92.74 (92.59)°, space group P2₁/c, Z = 2, R_g = 0.045 (0.058) for 2543 (2716) independent reflections. The resulting strongly puckered layer structure rather than of single octahedra consists of face-sharing M₂F₉ units, which are connected via the half of their remaining corners. The M? F distances vary from 195.1 to 212.0 (196.7 to 217.0) pm and show unusual high mean values of 203.7 (206.5) pm. Data for comparison and further details are discussed.     

Über Alkalimetall-Suboxide. VII. Das metallreichste Cäsiumoxid—Cs7O

On Alkali Metal Suboxides. VII. The Caesium Oxide with the Highest Metal Content, CS₇O Preparation, crystal growth and X-ray investigations with modified Guinier technique and single crystal diffractometer between 0° and ?170°C are reported for the compound Cs₇O. A simple nitrogen evaporator is described. — The structure of Cs₇O corresponds to the formula [Cs₁₁O₃]Cs₁₀. Single crystal investigations at ?20 and ?l70°C lead to nearly identical atomic distances within the “ionic cluster” Cs₁₁O₃, whereas distances between these clusters and within the oxygen free parts of the structure vary as in metallic caesium.     

Über Cs2Li2[GeO4]

About Cs₂Li₂[GeO₄] By heating of a well-ground mixture of the binary oxides CsO_0.55, Li₂O and GeO₂ (Cs:Li:Ge=2,6:2,2:1; Ni-tube; 600 °C; 49d) we got single crystals of Cs₂Li₂[GeO₄] for the first time. Cs₂Li₂[GeO₄] is isotypic to Rb₂Li₂[MO₄] [M = Si, Ti, Ge] [2] and Cs₂Li₂[MO₄] (M = Si, Ti) [3]: according to this Cs₂Li₂[GeO₄] crystallizes triclinic, in the spacegroup P1 with a = 968.7(4) pm, b = 586.0(2) pm, c = 571.4(2) pm, α = 92.71(4)°, β = 110.95(3)° and γ = 94.34(4)° (Guinier-Simon data), Z = 2. The structure was determined by four-circle diffractometer data (Ag? K_α ; 2381 I_o(hkl); R = 8,4%; R_w = 5.0%), parameters see text. Further the Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN) and the Mean Fictive Ionic Radii (MEFIR), have been calculated.     

Über die Matrixisolation von AsCl4F

Matrix Isolation of AsCl₄F The gasphase components during the sublimation of [AsCl₄]⁺[AsF₆]^? are characterized by means of mass and IR matrixisolation spectroscopy. The primary vaporization products are AsF₅ and the new halide AsCl₄F. The IR spectra of AsCl₄F and PCl₄F are compared and the calculated force constants are discussed. Other mixed halides of arsenic are formed under suitable conditions.     

Über Triphosphorsäurederivate des Cyanamids und des Harnstoffs

Triphosphoric Acid Derivatives of Cyanamide and Urea Cyanamidotriphosphate, P₃O₉NCN^5? ( I ), is obtained by ring opening reaction of the cyclotriphosphate ion, P₃O₉^3?, by cyanamide in alkaline solution. As a pseudochalcogeno-substituted triphosphate, I has similar properties like the triphosphate, P₃O₁₀^5? (Ca²⁺ sequestering; behaviour on acidimetric titration; X-ray powder diffraction of the sodium salt hydrates). In acidic solution I decomposes forming ureidotriphosphate with the anion P₃O₉NHCONH₂^4? ( II ) which cannot be directly obtained from cyclotriphosphate and urea. II is characterized by its chemical analysis, by paper chromatography, by its behaviour in acidic solution and by its IR and ³¹P-NMR spectra. Solid salts of I and II are prepared and the data of their Guinier diagrams are communicated.     

Über Chalkogenidhalogenide des Kupfers

Nine ternary chalcogenidehalides of copper could be synthesized under hydrothermal conditions from the resp. hydrogen halide solutions. They belong to the pseudobinary systems, formed between selenium and tellurium and the resp. Cu^I halide. In the selenium systems exist: CuISe₃, rhombohedral; CuBrSe₃, orthorhombic, and CuClSe₂, monoclinic. Two homologous series of tellurium compounds exist: CuXTe, tetragonal, and CuXTe₂, monoclinic (X ? Cl, Br, I). Thermodynamic data could be obtained for the selenium compounds using the Knudsen effusion method. The samples exhibit a temperature independant diamagnetism. All compounds can also be synthesized by reaction of stoichiometric amounts of Cu^I halide and selenium (300°C) or tellurium (350°C). The corresponding thiohalides could not be observed.     

Über ein Oxidchlorid des Calciums: Ca4OCl6

An Oxychloride of Calcium: Ca₄OCl₆ Ca₄OCl₆ (hexagonal, P6₃mc, Z = 2), a = 905.8(3), c = 686.3(4) pm, (R = 0.031) crystallizes as colourless needles from reducing melts (CaCl₂, Ca) that contain small amounts of ?oxygen”?. It contains ?isolated”? tetrahedral units [Ca₄O] and is isotypic with e.g., Ba₄OCl₆, Yb₄OCl₆ and K₆HgS₄. Ca₄OCl₆ does not form in the dehydration process of, for example, CaCl₂ · 6 H₂O.     

Über Kondensierte Phosphate des Melamins

Condensed Phosphates of Melamine The title compounds with the formulae (C₃H₆N₆)_n · H_n+2P_nO_3n+1 (linear phosphates, n = 2; 3) and (C₃H₆N₆ · HOP₃)_m (cyclic phosphates, m = 3; 4; 6; 8 and high polymeric phosphate) are obtained as crystalline hydrates by interaction of the corresponding sodium phosphates with stoichiometric amounts of melamine hydrochloride and hydrochloric acid or melamine hydrochloride in aqueous solution. With the exception of (C₃H₆N₆ · HPO₃)₄ · 6H₂O ( I ) these hydrates decompose at ～100°C forming a mixture of mono and diphosphate which transforms at ～200°C into pure melamine diphosphate and at ～250°C into melamine polyphosphate. In contrast to this I froms at ～100°C the anhydrous melamine tetrametaphosphate which converts at ～150°C into melamine polyphosphate. Melamine diphosphate and polyphosphate are also formed on heating melamine monophosphate C₃H₆N₆ · H₃PO₄.