Über Alkaliselenobismutate(III), mit einer Bemerkung zum Th3P4-Typ

About Alkali Seleno Bismuthates (III), with a Comment Regarding the Th₃P₄ Structure Type The synthesis and X-ray single crystal structure determination of the ternary selenides Rb₃BiSe₃, Cs₃BiSe₃, and RbK₂BiSe₃ are described. The compounds were synthesized via a reaction of Bi₂O₃ with the alkali carbonate in a selencharged hydrogen stream at 850°C. They crystallize in the Na₃AsS₃ structure type (space group P2₁3). In the discussion of the structure, the aristotypic Th₃P₄ structure is included.     

Die Kristallstruktur von Cs2PrO3, sowie über Cs2CeO3, Cs2TbO3, Rb2CeO3 und Rb2TbO3

Crystal Structure of Cs₂PrO₃ and also about Cs₂CeO₃, Cs₂TbO₃, Rb₂CeO₃, and Rb₂TbO₃ New prepared Cs₂PrO₃ (dark brown) is orthorhombic due to single crystal data, K₂PbO₃ type of structure (Cmc2₁) with a = 11.4₇, b = 7.72₂, c = 6.42₇ Å and Z = (4). Cs₂CeO₃ (colourless, a = 11.49₅, b = 7.75₃, c = 6.43₇ Å), Cs₂TbO₃ (red-brown, a = 11.3₇, b = 7.72₆, c = 6.14₂ Å), and the low-temperature form of (LT-) Rb₂TbO₃ (red-brown, a = 10.9₁, b = 7.39₀, c = 6.09₉ Å) are isotypic. Hitherto unknown HT-Rb₂CeO₃ (high-temperature form, colourless, a = 3.83₇, c = 18.4₇ Å, Z = 2, hexagonal) and “HT-Rb₂TbO₃” (red-brown, a = 3.77₃, c = 18.0₀ Å) correspond according to powder-data to the α-NaFeO₂ type of structure. Cs₂PrO₃ has been measured magnetically (100–300 K). The Madelung Part of Lattice Energy (MAPLE) is calculated and 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.     

Alkaline metal oxoantimonates(III), A3[SbO3] (A = K or Cs)

The two title trialkaline trioxoantimonates(III), tripotassium trioxoantimonate(III), K₃[SbO₃], (I), and tricaesium trioxo­antimonate(III), Cs₃[SbO₃], (II), crystallize in the cubic Na₃[AsS₃] structure type in space group P2₁3. The structures show discrete Ψ-tetrahedral [SbO₃]³⁻ anions with C_3v point-group symmetry. The Sb—O distances are 1.923 (4) Å in (I) and 1.928 (2) Å in (II), and the O—Sb—O bond angles are 99.5 (2)° in (I) and 100.4 (1)° in (II).     

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.     

Neue Oxocuprate (I). Über Cs3Cu5O4, Rb2KCu5O4, RbK2Cu5O4 und K3Cu5O4

New Oxocuprates(I). On Cs₃Cu₅O₄, Rb₂KCu₅O₄, RbK₂Cu₅O₄ and K₃Cu₅O₄ Cs₃Cu₅O₄ light yellow, powder as well as single crystals [a = 10.313(9), b = 7.630(1), c = 14.750(4) Å, β = 106.48(6)°], Rb₂KCu₅O₄ [a = 9.724(2), b = 7.443(0), c = 14.246(2) Å, β = 106.78(8)°], RbK₂Cu₅O₄ [a = 9.561(1), b = 7.411(0), c = 14.111(1) Å, β = 106.76(7)°] and K₃Cu₅O₄ [a = 9.422(1), b = 7.364(1), c = 13.995(2) Å, β = 107.00(2)°] are new prepared. The colour of the powders becomes lighter according to the sequence showed above. K₃Cu₅O₄ shows pale yellow. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Zur Kristallchemie der Oxometallate des Thoriums

The crystal chemistry of the valence stable Thorium (Th⁴⁺) shows in oxovanadates, ‐niobates, ‐molybdates, ‐tantalates etc. typical cationic property. It depends on the big size of the Th⁴⁺ ion in the order of r(Th⁴⁺) = 0.92 Å (C.N. = 6) up to r(Th⁴⁺) = 1.34 Å (C.N. = 12), comparable with the radii of alkaline and alkaline earth metals: r(Na⁺) = 1.02 Å (C.N. = 6) or r(K⁺) = 1.5 Å (C.N. = 8); r(Ca²⁺/Sr²⁺) = 1.1 Å/1.26 Å (C.N. = 8). There exists only one typical compound that may be of the oxothorate type with the composition NaK₃Th₂O₆. Na⁺ and K⁺ can be declared to be components of the cationic part of the crystal structure. In contrary, thorium and oxygen are common components of the anionic part of the crystal structure. From the point of view of the shared polyhedra (exclusively octahedra), NaK₃Th₂O₆ belongs to the thorium‐oxometallates too. The report on oxometallates of thorium shows compounds with one, two, four and five Th⁴⁺ atoms in combination with V⁵⁺, Nb⁵⁺, Ta⁵⁺ and Mo⁶⁺. W⁶⁺ is completely missing. Some of the Tantalates belong to the Jahnberg compounds, showing planar nets of corner shared pentagonal bipyramids. ThMO₄ and cationic mixed compounds, Th_1–xA_xMO₄, crystallize with the Scheelite (respectively Huttonite) structure and at least Th⁴⁺ is part of ordered and disordered perowskites showing more or less deviations from the cubic symmetry.     

Zur Kenntnis der Oxoberyllate der Alkalimetalle [1, 2]

On Oxoberyllates of the Alkali-Metals The existence of the phases K₂Be₂O₃ (2 forms), K₄BeO₃, Rb₂Be₃O₄, Rb₂Be₂O₃,Rb₄BeO₃, Cs₂Be₃O₄ and Cs₂BeO₂ is proved by powder-datas according to GUINIER -SIMON . In single crystal form we obtained Li₄BeO₃ [a = 5.49; b = 9.53; c = 4.93 Å; a = 114.₁; ß = 105.₀; γ = 106.₆°; triclinic], Na₂Be₂O₃ [;a = 6.32; b = 8.53; c = 2.71 Å; α = 107.₇; ß = 105.₅; γ = 78.₄°; triclinic], Na₆Be₂O₅ [a = 5.67₂; c = 10.2₁ Å; tetragonal] as also K₂BeO₂ [a = 7.09₈; b = 10.57₇; c = 5.70₆ Å; γ = 131.₃°; monoclinic] and Rb₂BeO₂ [a = 7.46₃; b = 11.17₀; c = 5.88₁ Å; γ = 131.₈°; monoclinic].     

Neue Fluorperowskite mit Cr‴ und Mn‴: A(B03Cr0.5)F3 und A(B05Mn0,5)F3; A,B=Alkalimetall

New fluoroperovskites with Cr^III and Mn^III: A(B_0.5Cr_0.5)F₃ and A(B_0.5Mn_0.5)F₃; A, B = alkali We obtained Cs₂KCrF₆ (a = 9.00₄ Å), Rb₂KCrF₆ (a = 8.81₇ Å), Rb₂NaCrF_e(a = 8.41₈ Å) (all green, K₂NaCrF₆-type) and Cs₂NaCrF₈ as well as Rb₂NaMnF₆ (tetragonally distorted K₂NaCrF₆-type; a = 8.36₅, c = 8.66₀ Å; F4/mmm), and Rb₂KMnF₆ and Cs₂NaMnF₆, all violet. Jahn-Teller-distortion and lattice energy of Rb₂NaMnF₆ and K₂NaMnF₆ are discussed.     

Zur Magnetochemie des zweiwertigen Silbers Neue Fluoroargentate(II): Cs2AgF4, Rb2AgF4 und K2AgF4

Magnetochemistry of Divalent Silver. New Fluoroargentates(II): Cs₂AgF₄, Rb₂AgF₄, and K₂AgF₄ Hitherto unknown blue compounds Rb₂AgF₄ and Cs₂AgF₄ are prepared. Guinier patterns show, that Cs₂AgF₄ cristallise in the K₂NiF₄ structure (a = 4.58₁, c = 14.19₂ Å). The structure of the Rb-compound is still unknown. The magnetic behaviour of K₂AgF₄, Rb₂AgF₄, and Cs₂AgF₄ is discussed.     

Zintl‐Verbindungen mit Gold und Germanium: M3AuGe4 mit M = K,Rb und Cs

Zintl‐Compounds with Gold and Germanium: M₃AuGe₄ with M = K, Rb, Cs Black, brittle single crystals of M₃AuGe₄ with M = K, Rb, Cs were synthesized by reactions of alkali metal azides (MN₃) with gold sponge and germanium powder at T = 1120 K. The structures of the compounds (space group Pmmn, Z = 2, K₃AuGe₄: a = 6.655(1)Å, b = 11.911(2)Å, c = 6.081(1)Å; Rb₃AuGe₄: a = 6.894(1)Å, b = 12.421(1)Å, c = 6.107(1)Å; Cs₃AuGe₄: a = 7.179(1)Å, b = 12.993(2)Å, c = 6.112(2)Å) were determined from X‐ray single‐crystal diffractometry data. The semiconducting compounds contain equation/tex2gif-stack-2.gif[AuGe₄]‐chains with P₄‐analogous Ge₄‐tetrahedra which are connected by μ₂‐bridging gold atoms in a distorted tetrahedral Ge‐coordination.     

Über Oxoniccolate(II) der Alkalimetalle:K2NiO2, Rb2NiO2 und Cs2NiO2

On Oxoniccolates(II) of Alkali Metals: K₂NiO₂, Rb₂NiO₂, and Cs₂SiO₂. The hitherto unknown K₂NiO₂ (dichroic single crystals: redviolet/green, a=3.95₃, c=12.85₃ Å), Rb₂NiO₂ (analogous yellowred/green, a=4.17₄, c=13.18₆ Å) and Cs₂NiO₂ (analogous: darkgreen/green, a=4.41₃, c=13.59₀ Å) have been obtained, which surprisingly crystallize in the tetragonal Na₂HgO₂-type of structure with [O–-Xi –-O]-dump-bells. The distance Ni –-O is very short: 1.68 Å. The K₂SiO₂-structure was determined using single crystal data, R=7.98% and R′=10.6% for 131 reflections hhl–- (h+3)hl. The magnetic datas for K₂NiO₂ and Cs₂NiO₂ obey the CURIE -WEISS -law (μ=3,0 μ_B. Θ ? ?30°K). The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Über Ordnungsvarianten des NaCl-Typs. Neue kubische Formen von NaMO2 (M=Sc,Y, Dy,Tm, Yb,Lu), K2MO3 Rb2MO3, (M = Ce,Pr, Th) und Cs2ThO3

On Ordered Variants of the NaCl Type of Structure: New Cubic Forms of NaMO₂ (M = Sc, Y, Dy, Tm, Yb, Lu), K₂MO₃, Rb₂MO₃ (M = Ce, Pr, Th), and Cs₂ThO₃ We obtained hithertoo unknown cubic forms of NaScO₂ (a = 4.52₅ Å), NaYO₂ (a = 4.79₁ Å), NaDyO₂ (a = 4.80₀ Å), NaTmO₂ (a = 4.74₃Å), NaYbO₂ (a = 4.73₀ Å), NaLuO₂ (a = 4.71₅ Å) [all colourless], K₂CeO₃ (a = 5.20₃ Å), K₂PrO₃ (a = 5.18₅ Å), K₂ThO₃ (a = 5.30₈ Å), Rb₂CeO₃ (a = 5.39₇ Å), Rb₂PrO₃ (a = 5.36₇ Å), Rb₂ThO₃ (a = 5.47₅ Å), and Cs₂ThO₃ (a = 5.70₄ Å) [colour see ins.] by heating mixtures of the binary oxides AO_x (A = Na, K, Rb, Cs) with active forms of M₂O₃, respectively. It is discussed MO₂, how one may understand the existence of the cubic forms, which according to powder data show a statistical distribution of cations (with different charge and ionic radius).     

Neues über K2[MnF6], Rb2[MnF6] und Cs2[MnF6]

News on K₂[MnF₆], Rb₂[MnF₆], and Cs₂[MnF₆] Cs₂[MnF₆] (a = 8.97₂ Å) and Rb₂[MnF₆] (a = 8.53₁ Å) as well as this with K₂[MnF₆] (a = 8.22₁ Å and hexagonal a = 5.72₂, c = 9.33₁ Å) form mixed crystals of the K₂PtCl₆ type of structure. Calculations of the Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, lead contrary to former assumptions to distances Mn? F of about 1.86 Å (CN 6).     

Neue Elpasolithvertreter mit CoIII: Cs2KCoF6, Rb2KCoF6, Rb2NaCoF6 (mit einer Notiz über Cs2NaCoF6)

New Elpasolithes with Co^III: Cs₂KCoF₆, Rb₂KCoF₆, Rb₂NaCoF₆ (with a Notice on Cs₂NaCoF₆) New prepared are the compounds Cs₂KCoF₆ (a = 8.97₉ Å), Rb₂KCoF₆ (a = 8.80₉ Å), Rb₂NaCoF₆ (a = 8.42₁ Å), all cubic Elpasolithes, as well as Cs₂NaCoF₆ (Cs₂NaCrF₆?type, hexagonal with a = 6.23, c = 30.32 Å) all of light blue colour. Cs₂KCoF₆ (72.7–299.7 K) and Rb₂KCoF₆ (71.4–298.0 K) have been measured magnetically. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Über Hexafluoroferrate(III): Cs2TlFeF6, Cs2KFeF6, Rb2KFeF6, Rb2NaFeF6 und Cs2NaFeF6

On Hexafluoroferrates(III): Cs₂TlFeF₆, Cs₂KFeF₆, Rb₂KFeF₆, Rb₂NaFeF₆, and Cs₂NaFeF₆ New prepared are the compounds Cs₂TlFeF₆ (a = 9.21₁ Å), Cs₂KFeF₆ (a = 9.04₁ Å), Rb₂KFeF₆ (a = 8.86₈ Å) and Rb₂NaFeF₆ (a = 8.46 ₄Å) all cubic Elpasolithes as well as Cs₂NaFeF₆ (Cs₂NaCrF₆?type, hexagonal with a = 6.28₁, c = 30.53₂ Å), all colourless. Cs₂KFeF₆ was measured magnetically (70–297,2 K). The spectra of reflection were measured (9000–36000 cm^?1). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Neue Hexafluoromolybdate(III). Cs2MMoF6, Rb2MMoF6, TI2MMoF6 (M = K,Na) und Cs2TIMof6. Mit einer Notiz über MoF3

Novel Hexafluoromolybdates(III): Cs₂MMoF₆, Rb₂MMoF₆, TI₂MMoF₆ (M = K, Na), and Cs₂TIMoF₆. With a Notice on MoF₃ MoF3, light yellow, hexag., a = b = 5.21, c = 14.41 Å, pure prepared by a new method, forms at higher temperatures with the corresponding Fluorides AF the hitherto unknown compounds Cs₂KMoF₆ (a = 9.2₀ Å), Cs₂TlMoF₆ (a = 9.39₂ Å). Rb₂KMoF₆ (a = 8.91₁ Å), Rb₂NaMoF₆ (a = 8.63₂ Å), Tl₂KMoF₆ (a = 8,97₇ Å), Tl₂NaMoF₆ (a = 8.64₉ Å) and K₂NaMoF₆ (a = 8.50₁ Å), all cubic Elpasolithes and all light yellow. The magnetic properties of MoF₃ (100.4–295.2 K) and Tl₂NaMoF₆ (81.4–251.3 K) are investigated. The spectra of reflection were measured (15000–36000 cm^?1). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Oxydationsprodukte intermetallischer Phasen. III. Tieftemperaturformen von K2Sn2O3 und Rb2Sn2O3 und eine Notiz über K2Ge2O3

Oxidation Products of Intermetallic Compounds. III. Low Temperature Forms of K₂Sn₂O₃ and Rb₂Sn₂O₃ and a Notice about K₂Ge₂O₃ By controlled oxidation of KSn (at 320°C) and RbSn (at 410°C) with O₂ the hitherto unknown low temperature forms of K₂Sn₂O₃ (a = 8.4100(8) Å) and Rb₂Sn₂O₃ (a = 8.6368(8) Å) are obtained, which are isotopic with cubic K₂Pb₂O₃. Oxidation at higher temperatures (at 510–5207°C) leads to the well-known HT-forms. The Madelung Part of Lattic Energie, MAPLE, is calculated for both compounds. K₂Pb₂O₃, Rb₂Pb₂O₃, Cs₂Pb₂O₃, and Cs₂Sn₂O₃ have been prepared too by oxidation of KPb, RbPb, CsPb, and CsSn. Oxidation of KGe (at 400°C) leads to the first oxogermanate(II), K₂Ge₂O₃ (cubic a = 8.339(1) Å, isotypic with K₂Pb₂O₃) together with K₆Ge₂O₇.     

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.