Über Perowskitphasen des Systems Ba2Y0,67U1−xWxO6

On Perovskite Phases of the System Ba₂Y_0,67U_1?xW_xO₆ A solid solution series is formed between the polymorphic perovskites Ba₂Y_0.67UO₆ and Ba₂Y_0.67WO₆ (cubic: a = 8.37₂ Å; hexagonal: a = 4× 5.88₁ Å and c = 4× 7.77₈ Å). The structure is cubic between x = 0.1 and 0.99 and for x > 0.95 hexagonal as well. Strong deviations from the ideal behaviour are detectabel with spectroscopic methods. The shape of the UO₆ and WO₆ octahedrons experiences only minor changes within the series.     

Über Oxocadmate: K2Cd2O3

New obtained is K₂Cd₂O₃ (brownish red), which – according to single crystal work [487 h 01–h 41, Mo? Kα, R = 9.7₃%, R′ = 10.7₆%] – crystallises monoclinic with a = 6.41₇, b = 6.72₃, c = 6.58₆ Å, β = 116.0° in P2₁/c–C [K⁺, Cd²⁺ and O(1)^2? in 4(e), O(2)^2? in 2(a)] and is isotypic with Na₂Zn₂O₃. [Parameters see text]. The Madelung Part of Lattice Energy is calculated and discussed.     

Über Na2PrO3 und Na2TbO3

On Na₂PrO₃ and Na₂TbO₃ Using an exchange reaction of Na₂O with Li₈TbO₆ (Na : Tb = 2.1 : 1; au-tube; 750°C, 30 d) yellow-orange colored single crystals of Na₂TbO₃ could be prepared for the first time. Na₂TbO₃ crystallizes monoclinic in C2/c (Z = 8; a = 576.92(6), b = 1001.27(9), c = 1117.91(14) pm, β = 99.98(1)°). According to four-circle data the Li₂SnO₃-type of structure is adopted (PW 1100, MoKα , 1935 I₀ (hkl), R = 4.86%, R_w = 3.63% for all 928 unique reflexions). By a similar exchange reaction of Na₂O with Li₈PrO₆ for the first time single crystals of Na₂PrO₃ could be prepared, too (Na : Pr = 2.2 : 1; au-tube; 700°C; 23 d). The structure determination reveils that there is a variant of the NaCl-type of structure, which ressembles to the Li₂SnO₃-type of structure (PW 1100, MoKα , 2199 I₀ (hkl)), R = 8.88%, R_w = 5.21% for all 947 unique reflexions; C2/c, Z = 8, a = 678.78(5), b = 977.47(7), c = 1080.38(9) pm, β = 108,4(1)°. In contrast to Na₂TbO₃ there are no layers according to NaO(Na_1/3Tb_2/3)O. All octahedral intersticies are occupied systematically with Pr⁴⁺ and Na⁺ : (Na_2/3Pr_1/3)O(Na_2/3Pr_1/3)O.     

Über Oxothorate der Alkalimetalle. Zur Kenntnis von K3NaTh2O6

On Oxothorates of the Alkaline Metals: K₃NaTh₂O₆ For a first time single crystals of a (in addition: new) oxothorate were prepared starting with the binary oxides [1 200°C, 4d, then 1 300°C, 5d, Ni-bomb; powder: 650°C, 10d, Ag-bomb]. The colourless, transparent single crystals are monoclinic, C2/c, a = 629.64 pm, b = 1 089.93 pm, c = 1 259.75 pm, β = 99.66°, z = 4, D_x = 5.458 g cm_?3 and D_pyc = 5.456 gcm_?3. It is an ordered variant of the NaCl-type; MoKα, fourcircle diffractometer data (PW 1100), R = 7.6₇ and R_w = 7.3₅% for 1 083 of 1 236 I₀ (hkl). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Über eine neue Modifikation des Na2C2

On a New Modification of Na₂C₂ On heating NaC₂H to temperatures between 80 °C and 150 °C in vacuum two coexisting modifications of Na₂C₂ are observed, as was shown by temperature dependent X‐ray powder diffraction. The known modification I (I4₁/acd, Z = 8) and a previously unknown modification II could be identified, which is isotypic to Li₂C₂ (Rb₂O₂ structure type, Immm, Z = 2). Modification II is also stable on cooling to room temperature, but a complete conversion of NaC₂H to Na₂C₂‐II could not be achieved up to now. Heating to temperatures above 150 °C leads to a complete conversion of Na₂C₂‐II to Na₂C₂‐I. According to MAPLE calculations Na₂C₂‐I represents the thermodynamically stable modification at room temperature.     

Neue Oxogallate der Alkalimetalle: Über K6[Ga2O6] und Rb6[Ga2O6], sowie Na3GaO3 und Cs6[Ga2O6]

New Oxogallates of Alkaline Metals: On K₆[Ga₂O₆] and Rb₆[Ga₂O₆] as well as Na₃GaO₃ and Cs₆[Ga₂O₆] Due to powder and single crystal data K₆[Ga₂O₆] a = 7.09₉; b = 11.11₆; c = 6.48₄ Å; ß = 101.6₆° and Rb₆[Ga₂O₆] a = 7.39₃; b = 11.47₅; c = 6.79₈ Å; ß = 103.5° crystallize isotypic with K₆[Fe₂O₆]; space group C2/m-C₃^2h; As well has been prepared the hitherto unknown Na₃GaO₃ a = 11.48, b = 10.82, c = 6.13 Å, space-group Imcm or I2cm Z = 8; and Cs₆[Ga₂O₆] a = 7.2₆, b = 12.1, c = 7.6₈ Å, ß = 105°, Z = 4, space-group P2₁/a.     

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).     

Die Polytherme des Quinären Systems Na+, K+, Mg2+/Cl−, SO//H2O im Bereich von +25° bis −10°C

Polythermal Curves of the Quinary System Na⁺, K⁺, Mg²⁺/Cl^?, SO//H₂O in Range between +25°C and ?10°C Proceeding from the 0°C, ?5°C and ?10°C isothermal curves of the quinary system Na⁺, K⁺, Mg²⁺/C1^?, SO//H₂O with saturation at NaCl, KCl, and carnallite, respectively, the polythermal curve is represented between 25°C and ?10°C. Within the new defined range of the polythermal curve the invariant five-salt-paragenesis NaCI, KCI, Glauber's salt (Na₂SO₄ · 10 H₂O), bitter salt (MgSO₄ · 7 H₂O), Schoenite (K₂SO₄ · MgSO₄ · 6 H₂O) can be found at ?7,2°C. It represents also the lowest temperature of formation of Schoenite in this system. It was necessary, moreover, to reconsider further univariant and invariant equilibrium solutions in the range between 25° and 0°C.     

Über die Kristallstrukturen von CH3PF2H+AsF6− und CH3PF2H+SbF6− und eine einfache Darstellung von CH3PF2

On the Crystal Structures of CH₃PF₂H⁺AsF₆^? and CH₃PF₂H⁺SbF₆^? and a simple Method for Preparation of CH₃PF₂ A simple method for preparation of CH₃PF₂ from CH₃PCl₂ is reported. The phosphonium salts CH₃PF₂H⁺MF₆^? are obtained by the reaction of CH₃PCl₂ with superacidic systems HF/MF₅ (M = As, Sb). CH₃PF₂H⁺SbF₆^? crystallizes in the space group P1 with a = 548.4(4) pm, b = 695.5(8) pm, c = 960.2(9) pm, α = 94.68(5)°, β = 97.19(6)°, γ = 94.41(6)° and Z = 2. CH₃PF₂H⁺SbF₆^? crystallizes in P1 with a = 554.3(3), b = 724.2(4), c = 970.4(5), α = 94.73(4)°, β = 96.14(5)°, γ = 95.30(4)°.     

Über die quasi-binären Systeme NaNO2/Na2O und NaCN/Na2O. Phasendiagramme und Natrium-Ionenleitung in Na3O(NO2) und Na3O(CN)

On the Quasi-Binary Systems NaNO₂/Na₂O and NaCN/Na₂O. Phase Diagrams and Sodium Ion Conductivity of Na₃O(NO₂) and Na₃O(CN) Measurements of the electrical conductivities of Na₃O(NO₂) and Na₃O(CN) show sharp increases in conductivity at temperatures between 200° and 250°C, According to the phase diagrams of the quasi-binary systems NaNO₂/Na₂O and NaCN/Na₂O this is not an effect established by fusion. It seems to be a consequence of a “melting” of the sodium sublattice or the rotational disorder of complex anions.     

Über Verbindungen des Typs Ba2BIIIOsVO6

Compounds of Type Ba₂B^IIIOs^VO₆ The black perovskites of type Ba₂B^IIIOs^VO₆ crystallize cubic (B^III ? Pr, Nd, Sm—Lu, Y) and rhombohedral (B^III ? La) respectively; the cell volumina decrease linearily with (r_BIII)³. Intensity calculations on powder data for Ba₂YOsO₆ (space group Fm3m—O) and Ba₂LaOsO₆ (space group R3m—D) gave the intensity related R′ values of 4.6% and 5.0% respectively. The results of the vibrational spectroscopic investigations are reported in common with the bond orders, M? O distances and mean amplitudes and compared with the corresponding values of the series Ba₂B^IIIIr^VO₆ and Ba₂B^IIIRu^VO₆.     

Über Alkali-hexachlorochromate(III): Na3CrCl6

Alkali-hexachlorochromates(III): Na₃CrCl₆ X-ray investigations on single crystals yielded for Na₃CrCl₆ a trigonal structure: space group P3 1c; a = 682.0(3) pm; c = 1203.4(5) pm; Z = 2. In a hexagonal-close arrangement of Cl^? ions, 2/3 of the octahedral holes are occupied orderly by Na⁺ and Cr³⁺ ions. The Na compounds of V³⁺ and Mo³⁺ are isotypic. The chlorochromates with K and Rb are crystallizing with the K₃MoCl₆ structure according to X-ray photos of powders. The alkali metal ions habe the C.N. 8 or 11 related to the chloride ions. These compounds and elpasolithes A₂BCrCl₆ (A = Cs? K; B = Rb? Na) can be treated in the same way with the concept of tolerance factors as it is known for the chloro-perovskites AMCl₃. For all compounds the temperatures of phase transitions were determined by DTA. Some structures could be solved from high-temperature-Guinier-patterns, by comparing them with patterns of substances with known structures.     

Zur Möglichkeit der Berechnung des Chemischen Transportverhaltens ternärer und komplizierterer Bodenkörper

On a Possibility of Calculation of the Chemical Transport Behaviour of Ternary and More Complicated Solids Relations are deduced in order to describe the transport behaviour of phases with a homogeniety range or of several solid phases in equilibrium in ternary and more complicated systems. In analogy to binary systems the transport behaviour can be predicted on the base of a thermodynamic analysis of the heterogeneous equilibria.     

Über die Alkaliselenoarsenate(III) KAsSe3 · H2O,RbAsSe3 · 1/2 H2O und CsAsSe3 · 1/2 H2O

On the Alkali Selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O The alkali selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O have been prepared by hydrothermal reaction of the respective alkali carbonate with As₂Se₃ at a temperature of 135°C. Their X-ray structural analyses demonstrated that the compounds contain polyselenoarsenate(III) anions (AsSe₃^?)_n, in wich the basic units are ψ-AsSe₃ tetrahedra, which are linked together through Se? Se bonds into infinite zweier single chains. The Rb and Cs salts are isotypic.     

Über Glasbildung und Eigenschaften von Chalkogenidsystemen. XIII. Über die Verbindungen Na6Ge2S6 · 4 CH3OH und Na6Ge2Se6 · 4 CH3OH

Glass Formation and Properties of Chalcogenide Systems. XIII. On the Compounds Na₆Ge₂S₆ · 4 CH₃OH and Na₆Ge₂Se₆ · 4 CH₃OH The glasses Ge₂S₃ and Ge₂Se₃ are soluble in solutions of Na₂S or Na₂Se in CH₃OH forming Na₆Ge₂S₆ · 4 CH₃OH and Na₆Ge₂Se₆ · 4 CH₃OH. On heating the CH₃OH-free substances are formed. From the i.r. and Raman spectra can de seen that the structure of the ions Ge₂S, Ge₂Se, P₂S₆^4?, and of Si₂Cl₆ is of the same type. The formation of the compounds can be regarded as a chemical proof for the existence of [Ge₂S₆] and [Ge₂Se₆] units as structural groups in the glasses Ge₂S₃ and Ge₂Se₃.     

Alkalioxoargentate(I). Über Na3AgO2

Oxoargentates(I) of Alkali Metals. On Na₃AgO₂ Na₃AgO₂ has been prepared anew (light pale-yellow powder samples; clear transparent single crystals). It crystallizes orthorhombic (space group Ibam) with a = 5.46₃, b = 10.92₆, c = 5.92₆ Å, Z = 4, d_rö = 3.94 g X cm^?3, d_pyk = 3.89 g X cm^?3; parameters are given in the text. The structure of Na₃AgO₂, marked by linear “dumb-bells” [O? Ag? O], d(Ag→O) = 2.09 Å is a novel variant of Na₂O. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, have been calculated and are discussed.     

Über Hexafluorovanadate(III). Cs2MVF6 und Rb2MVF6 (MTl,K und Na); mit einer Bemerkung über Na3VF6

On Hexafluorovanadates(III). Cs₂MVF₆ and Rb₂MVF₆ (M?Tl, K. and Na); with a Remark on Na₃VF₆ By heating the binary fluorides in a closed system we obtained Cs₂TlVF₆ (a = 9.23₄ Å), Cs₂KVF₆ (a = 9.04₇ Å), Rb₂KVF₆ (a = 8.85₅ Å) and Rb₂NaVF₆ (a = 8.46₈ Å), all cubic Elpasolithes of soft green colour as well as Cs₂NaVF₆ (hexagonal a = 6.24 Å, c = 30.58 Å, isotypic with Cs₂NaCrF₆) and Na₃VF₆ (monoclinic a = 5.51₃ Å, b = 5.72₁ Å, c = 7.96₃ Å, β = 90.4₇°, isotypic with Na₃AlF₆). VF₃ (3.0–296.2°K), Cs₂TlVF₆, Cs₂KVF₆ and Rb₂KVF₆ (all from 70–299°K) have been measured magnetically. The spectra of reflection in the range of 9 000 to 33 000 cm^?1 of VF₃ and the new quaternary fluorides are measured and discussed. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Über neue Verbindungen Cs2NaMF6 und K2NaMF6 sowie über Cs2KMnF6

Newly prepared are the cubic derivatives of the perovskite type of structure: K₂NaInF₆ (a = 8.56₀ Å), K₂NaTlF₆ (8.66₈), K₂NaScF₆ (8.48₂), K₂NaYF₆ (8.71₁), Cs₂NaInF₆ (8.90₅), Cs₂NaTiF₆ (8.99₅), Cs₂NaScF₆ (8.85₃), all colourless, as well as K₂NaCuF₆ (8.20₃ Å, green) and Cs₂KMnF₆ (tetragonal, a = 8.93₃; c = 9.26₅ Å, violett). K₂NaCuF₆ [μ = 2.8₇ μ_B, θ = ?17°] and Cs₂KMnF₆ [;μ = 4.8₈ μ_B, θ = ?5°] obey the Curie-Weiss law. The volume chemistry of the compounds is discussed in detail.