Über Oxostannate(II). II. Zur Kenntnis von Cs2Sn2O3

On Oxostannates(II). II. On the Knowledge of Cs₂Sn₂O₃ Cs₂Sn₂O₃ has been prepared for the first time by heating of mixtures of CsO_0.46 and SnO with Cs:Sn = 1.0:1 [under Argon, Al₂O₃ or Ag cylinders, 480°C, 3 d or 18 d as pale light yellow powder or light yellow transparent single crystals, respectively]. According to four-circle-diffractometer data [955 of 1199 I₀(hkl), Mo-Kα, not corrected for absorption, R = 8.1₇%, R_w = 7.9₇%] the compound crystallizes in Pnma with a = 13.70₈; b = 6.09₈; c = 8.92₁ Å, Z = 4, d_pyk = 4.84 g · cm^?3, d_calc = 4.91 g · cm^?3. Parameters see text. Cs₂Sn₂O₃ has a layer structure like K₂Sn₂O₃ but with an undulated instead of a flat O₃ part of the structure and different coordination of Cs versus O.     

Über Oxostannate(II). I. Zur Kenntnis von K2Sn2O3

On Oxostannates(II). I. Information on K₂Sn₂O₃ Hitherto unknown K₂Sn₂O₃ was obtained by heating mixtures of binary Oxides [KO_0.48 + SnO, K:Sn = 1.1:1] under Argon [Al₂O₃ cylinders, 550°C, 24 h or 7 d] as yellow powder or brownish-yellow single crystals, respectively. It crystallizes trigonal-rhombohedral in R3m—D, with a = 6.00₁ Å, c = 14.32₇ Å, Z = 3, d_rö = 4.05 and d_pyk = 3.98 gcm^?3, positions are given in text, R = 2.1₁% for 219 hkl (MoKα, 4-circle diffractometer data).     

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.     

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.     

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 K2PbO3 [1,2] Rb2PbO3 [3–5] und Cs2PbO3 [6,7]

On the Oxides A₂PbO₃ (A = K, Rb, Cs) The oxides A₂PbO₃ (A = K, Rb, Cs) have been reinvestigated [four-circle diffractometer PW 1100 (Fa. Philips), all particles ?anisotropically”? refined, parameters see text]. The structural features are confirmed, whereas the results on space group and parameters have to be partially corrected.     

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 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.     

Über die Systeme Arsen(III)-chlorid–Arsen(III)-oxid und Arsen(III)-chlorid–Wasser (AsCl3 – As2O3 und AsCl3 – H2O)

In the system AsCl₃ – As₂O₃ are found the crystalline solids AsOCl and As₄O₅Cl₂, in the system AsC1₃–H₂O: As₄O₆ and AsOCl. The phase diagram AsCl₃–H₂O is determined at 20°C.     

Über die Dihydrogenphosphide der Alkalimetalle,MPH2 mit M ≙ Li,Na, K,Rb und Cs

Dihydrogenphosphides of Alkali Metals, MPH₂ (M ? Li, Na, K, Rb, Cs) The dihydrogenphosphides from lithium to cesium were obtained by the reaction of PH₃ with the corresponding solutions of the metals or the metal amides in ammonia. The compounds were examined by X-ray, IR-spectroscopic, and thermochemical techniques. LiPH₂ is not stable at room temperature, while evolving PH₃ it decomposes to yellow products. NaPH₂ is a stable, white compound; above 393 K it decomposes associated with discolouring. KPH₂ and RbPH₂ exist in the region from 110 K to ～400 K in three crystalline forms. Its high-temperature modification is of the sodium chloride-type structure; a monoclinic deformation occurs with decreasing temperature. DSC-measurements revealed a further low temperature form. CsPH₂ crystallizes in the CsCl-type structure between 110 K and ～400 K.     

Über die Trithiocyanatoargentate Rb2Ag(SCN)3 und Cs2Ag(SCN)3

On the Trithiocyanatoargentates Rb₂Ag(SCN)₃ and Cs₂Ag(SCN)₃ The trithiocyanatoargentates Rb₂Ag(SCN)₃ and CsAg(SCN)₃ are obtained by crystallization from highly concentrated aqueous solutions. In the crystal structures the Ag atoms are surrounded tetrahedrally by the S atoms of 4 SCN groups. These Ag(SCN)₄ tetrahedra are connected by common corners to polymer \documentclass{article}\pagestyle{empty}\begin{document}$ {}_\infty ^1 \left[{{\rm Ag}\left({{\rm SCN}} \right)_2 \left({{\rm SCN}_{2/2}} \right)} \right] $\end{document}¹[Ag(SCN)₂(SCN)_2/2] anion in Rb₂Ag(SCN)₃, whereas dimeric Ag₂(SCN)₆ anions were found in the Cs compound.     

Über Cs2TlBr5 – ein Pentabromothallat (III) mit tetraedrischen TlBr4− - und oktaedrischen TlBr63− -Anionen

On Cs₂TlBr₅ — a Pentabromothallat (III) with Tetrahedral TlBr₄^? and Octahedral TlBr₆^3? Anions Cs₂TlBr₅ has been synthesized by crystallization from aqueous TlBr₃/CsBr solutions. The orthorhombic structure (a = 1330.2(11); b = 777.0(3); c = 2349.3(6) pm; Z = 8, space group Pnma-Nr. 62) contains isolated tetrahedral TlBr₄- and octahedral TlBr₆^3? anions which are packed together with the Cs⁺ cations in an anti-CaWO₄ arrangement. At 260°C Cs₂TlBr₅ decomposes irreversibly to Cs₃Tl₂Br₉ and CsBr.     

Einkristallstrukturbestimmungen an KBiO2 und RbBiO2 und ein kristallchemischer Vergleich der Alkalimetallbismutate(III) vom Typ MBiO2 (M = Na,K, Rb,Cs)

Single Crystal Structure Determination on KBiO₂ and RbBiO₂ and a Crystal Chemical Comparison of MBiO₂ (M = Na, K, Rb, Cs) Single crystals of KBiO₂ (colourless) and RbBiO₂ (colourless) were obtained by solid state reaction of the respective binary metal oxides. Both crystal structures (KBiO₂: C2/c; a = 783.13(9), b = 790.92(1), c = 596.86(8) pm, β = 124.81(1)°; Z = 4; 445 diffractometer data; R₁ = 0.027; wR² = 0.069; RbBiO₂: C2/c; a = 806.20(5), b = 838.88(4), c = 598.14(4) pm, β = 123.68(1)°; Z = 4; 289 diffractometer data; R₁ = 0.040; wR² = 0.101) reveal infinite [BiO₂]-chains extending along the [0 0 1] direction. The compounds are isostructural with NaBiO₂ and CsBiO₂.     

K3SbSe3, Rb3SbSe3 und Cs3SbSe3 – Synthese und Kristallstruktur

K₃SbSe₃, Rb₃SbSe₃, and Cs₃SbSe₃ – Synthesis and Crystal Structure The compounds K₃SbSe₃, Rb₃SbSe₃ and Cs₃SbSe₃ were synthesized by heating mixtures of Sb₂O₃ and an alkalicarbonate in a stream of hydrogen saturated by selenium in a temperature range between 750 °C and 800 °C. The compounds crystallize isostructural with Na₃AsS₃. A comparison of atomic distances and bond angles with those of the isostructural arsenic and bismuth compounds shows the effect of lone pairs.     

K4PbO4 und K4GeO4 – ein Vergleich

K₄PbO₄ and K₄GeO₄ — a Comparison The question is: In which case are two compounds isotypic? The structures of K₄PbO₄ and K₄GeO₄ are derived using ?Schlegelprojektionen”? (reduced atomic distances and angles) and ?Erweiterte Schlegeldiagramme”? of the anions: O1, O2, O3 and O4. The difference is pointed out and discussed. For both compounds the interatomic distances are listed.     

Über Oxostannate(II). V. Na4[SnO3] – das erste Oxostannat(II) mit „Inselstruktur”︁

On Oxostannates(II). V. Na₄[SnO₃] – The First Oxostannate (II) with Island Structure The new oxid Na₄SnO₃ (yellow, transparant single crystals) has been prepared by heating of mixtures of: 1. NaO_0.45 and SnO (Na:Sn²⁺ = 4.1:1; Ag-cylinders; 600–730°C, 7–66 d); 2. NaO_0.45′ SnO₂ and Sn^±0 (Na:Sn⁴⁺:Sn^±0 = 8.2:1:1; Ag-cylinders; 650–680°C, 2–66 d); 3. NaO_0.45′ Na₂SnO₃ and Sn^±0 (Na:Na₂SnO₃:Sn^±0 = 6.1:1:1; Ag-cylinders; 650–670°C, 5 d). Na₄SnO₃:804 I₀(hkl); four circle diffractometer PW 1100; ω-scan; MoKα; R = 5.14%; R_w = 4.64%; monoclin, Cc? C; a = 582.77(11), b = 1667.44(24), c = 589.42(10) pm, β = 110.187(13)°; d_x = 3.20 g/cm³; d_pyk = 3.19 g/cm³; Z = 4; parameter look for text. It is a NaCl-variant with systemathical blanks of the anion part and “isolated” groups of [SnO₃]. \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm N}\mathop {\rm a}\limits^{\rm 1} $\end{document} has the uncommon coordination number 2. The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated. The structure is described using ?Erweiterte Schlegeldiagramme”?.     

Über Alkalimetallmanganchalkogenide A2MnX2 mit A K,Rb oder Cs und X S,Se oder Te

Inhaltsübersicht. Die Verbindungen K₂MnS₂, Rb₂MnS₂, Cs₂MnS₂, K₂MnSe₂, Rb₂MnSe₂, Cs₂MnSe₂, K₂MnTe₂, Rb₂MnTe₂ und Cs₂MnTe₂ wurden durch Umsetzungen von Alkalimetall-carbonaten mit Mangan bzw. Mangantellurid in einem mit Chalkogen beladenen Wasserstoffstrom erhalten. Kristallstrukturuntersuchungen an Einkristallen ergaben, daß alle neun Verbindungen isotyp kristallisieren (K₂ZnO₂-Typ, Raumgruppe Ibam). Untersuchungen zum magnetischen Verhalten zeigen antiferromagnetische Kopplungen der Manganionen in den [MnX_4/2^2–]-Ketten, On Alkali Metal Manganese Chalcogenides A₂MnX₂ with A K, Rb, or Cs and X S, Se, or Te The compounds K₂MnS₂, Rb₂MnS₂, Cs₂MnS₂, K₂MnSe₂, Rb₂MnSe₂, Cs₂MnSe₂, K₂MnTe₂, Rb₂MnTe₂, and Cs₂MnTe₂ were synthesized by the reaction of alkali metal carbonates with Mn or MnTe in a stream of hydrogen charged with chalcogen. Structural investigations on single crystals show that all nine compounds crystallize in isotypic atomic arrangements (K₂ZnO₂ type, space group Ibam). The magnetic behaviour indicates antiferromagnetic interactions of the manganese ions within the [MnX_1/2^2–] chains.     

Übergangsmetallchalkogenverbindungen. Über K2MoOS3 und K2WOS3 und ihre Reaktion mit Selenwasserstoff zu Dithiomonoselenomolybdaten und -wolframaten. Röntgenkristallographische Daten von Cs2MoOS2Se und Cs2WOS2Se

The preparation and properties of K₂MoOS₃ and K₂WOS₃ are reported. During the reaction of these salts in aqueous solution with H₂Se in the presence of Cs⁺ the compounds Cs₂MoOS₂Se and Cs₂WOS₂Se are formed. (For X-Ray-data see “Inhaltsübersicht”).     

Über Oxoplumbate(IV).IDie Kristallstruktur von Rb2PbO3

Rb₂PbO₃ [single crystals, 244 (hkl)] crystallises orthorhombic [D? Pmcn] with a = 10.8, b = 7.49, c = 5.98 Å [Z = 4, d_pyk = 5.69, d_rö = 5.80 g · cm^?3], Rb in 8(d) Pb in 4 (c), O_I in 4 (c). The parameters are shown in table 2. The MADELUNG Part of Lattice Energy of Rb₂RBO₃ and structurally related models are calculated and discussed in detail. Characteristic for the structure are ldimensional chains consisting of alternatingly directed pseudo-tetragonal pyramids, ∞¹[PbO₁O_4/2], connected via common basis edges.