Darstellung und Kristallstruktur der Dialkalimetalltrichalkogenide Rb2S3, Rb2Se3, Cs2S3 und Cs2Se3

Preparation and Crystal Structure of the Dialkali Metal Trichalcogenides Rb₂S₃, Rb₂Se₃, Cs₂S₃, and Cs₂Se₃ Crystalline products were obtained by the reaction of the pure alkali metals with the chalcogens in the molar ratio 2:3 in liquid ammonia at pressures up to 3000 bar and temperatures around 600 K. The substances crystallize in the K₂S₃ type structure (space group Cmc2₁(NO. 36)). Unit cell constants see ?Inhaltsübersicht”?. The characteristic feature of this structure are bent polyanions X₃^2?:(X = S,Se). The new described compounds are compared with the other known alkali metal trichalcogenides.     

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.     

Die Kristallstruktur von Kalium-trithiowolframat-chlorid K3(WOS3)Cl

A recently prepared new thiotungstate has been characterized by three-dimensional X-ray structure analysis, to be a double salt, containing K₂WOS₃ and KCl in equimolar proportions: potassium trithiotungstate chloride, K₃(WOS₃)Cl. Space group: Pca2₁ with a = 12.507, b = 6.317, c = 12,371 Å, Z = 4. The compound represents a new structure type with stoichiometry M^I₂XY₄ · M^IZ. Besides isolated tetrahedral WOS₃^2- ions (bond lengths W–O 1.760 Å, W–S 2.208, 2.197, 2.196 Å) the structure contains Cl^? ions octahedrally co-ordinated by K⁺, the K⁺ ions having 5S + 10 + 2Cl as neighbours. The dimensions of the WOS₃^2? ions in this compound show that, as in other transition metal oxo-, thio- and selenoanions, strong π bonding is present, the W–S bonds taking part in the π bond system.     

Röntgenographische Untersuchungen und Strukturchemie von Chalkogenomolybdaten und -wolframaten. II

X-Ray Investigations and Structure Chemistry of Chalkogenomolybdates and -tungstates. II. The chalkogenomolybdates and -tungstates (NH₄)₂MoS₃Se, (NH₄)₂MoS₂Se₂, (NH₄)₂MoSSe₃, (NH₄)₂WSSe₃, Cs₂MoS₂Se, Cs₂MoS₂Se, Cs₂MoSSe₃, Cs₂WSSe₃, Cs₂MoOS₂Se, Cs₂WOS₂Se, Cs₂MoOSSe₂, and Cs₂WOSSe₂ are investigated by means of X-ray powder diffractometry. All compounds crystallize orthorhombic in spacegroup D? Pnma and are isomorphous with β-K₂SO₄. Systematic relations between lattice constants and occupation of atomic positions in the unit cell are discussed.     

Die Kristallstruktur von K2S3 und K2Se3

The Crystal Structure of K₂S₃ and K₂Se₃ Well formed crystals of K₂S₃ and K₂Se₃ were obtained by reaction of the elements in liquid ammonia at 500 bar and 150°C. The substances are both orthorhombic, space group Cmc2₁. Cell constants are: The structure contains S₃^2?(Se₃^2?) polyanions, with S? S? S(Se? Se? Se) angles of 105.4(102.5)°. The S? S(Se? Se) distance is 2.083(2.383) Å.     

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.     

Die Antimonid–Triantimonidometallate(III) Cs6K3Sb[AlSb3] und Cs6K3Sb[GaSb3]

The Antimonide Triantimonidometallates(III) Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] The novel compounds Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] are formed from stoichiometric mixtures of Cs, AlSb (GaSb) and KSb in sealed niobium ampoules at 950 K. The hexagonal structures are especially characterized by one-dimensional rod packings ¹∞[Cs₆K₃Sb] which are formed from columns of condensed (Cs₆K_6/2) icosahedra. The icosahedra are centered by Sb^3-? anions. The trigonal planar anions [AlSb₃]^6-? and [GaSb₃]^6-? are embedded between the icosahedra columns, and they are coordinated by alkali metal atoms. The FIR spectra were assigned to the vibrations of the [MSb₃]^6-? anions, with respect to the 6 m2-D_3h symmetry. (P6₃/mmc, No. 194; a = 1101.7 and 1097.2 pm; c = 1158.9 and 1150.1 pm; Z = 2; Single crystal data: 574 and 546 reflections; R = 0.073 and 0.029. Distances:d(Al? Sb) = 265.4 pm; d(Ga? Sb) = 265.1 pm; d(Sb? Cs) = 401.6–423.0 pm; d(Sb? K) = 358.6–367.3 pm).     

Die Kristallstruktur von Cs2S. mit einer Bemerkung über Cs2Se,Cs2Te,Rb2Se und Rb2Te

The Crystal Structure of Cs₂S and a Remark about Cs₂Se, Cs₂Te, Rb₂Se, and Rb₂Te Cs₂S crystallizes orthorhombic, a = 8.57₁, b = 5.38₃, c = 10.3₉ Å, Z = 4, d_rö = 4.13, d_pyk = 4.19 g · cm^?3, D–Pnma with \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm Cs}}\limits^|,\mathop {{\rm Cs}}\limits^\parallel $\end{document} and S in 4(c) each, for parameter see text. It is R = 10,4% for 202 of 222 possible reflexes. There is a sequence of S^2? corresponding to the hexagonal closest packing of sphares. Cs occupies half of “tetrahedron” and all “octahedron vacancies”; the deviation of \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm Cs}}\limits^|, $\end{document} in ?oktahedron vacancies”? is noticeable. Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

Elektronenüberführungs-, IR-, RAMAN- und Photoelektronenspektren sowie röntgenographische Untersuchungen von Tl2MO2S2 Tl2MOS3und TB2MS4 (MMo,W) sowie Photoelektronenspektren zahlreicher Übergangsmetallverbindungen zum Vergleich

The electron transfer, i. r., RAMAN and photoelectron spectra and the powder diagrams of Tl₂MO₂S₂, TI₂MOS₃ Tl₂MS₄ (M = Mo, W) and, in comparison, the photoelectron spectra of some other transition metal compounds The electron transfer, i. r., RAMAN and photoelectron spectra and the powder diagrams of Tl₂MoO₂S₂, Tl₂WO₂S₂, Tl₂MoOS₃, Tl₂WOS₃, Tl₂MoS₄ and Tl₂WS₄ are reported and discussed. The different methods allow a discussion of the strong polarising effect of the Tl(I) cation on the anions. For the purpose of comparison the photoelectron spectra of the salts Tl₃MX₄ (M = V, Nb, Ta; X = S, Se); Tl₂MO₄ (M = Mo, W); Cs₂MX₄, (M = Mo, W; X = S, Se) and other similar salts were also measured.     

Über neuartige Chalkogenometallate des Typs A(MVIOS3)SH und AI[MVIS3(SH)] (M = Mo,W)

Novel Chalkogeno Metallates of the Type A (M^VIOS₃)SH and A^I[M^VIS₃(SH)] (M = Mo, W) The preparation and properties of the salts K₃(MoOS₃)SH and K₃(WOS₃)SH are reported. The compounds contain isolated MOS₃^2? anions in the lattice and are considered as double salts. They are crystallizing orthorhombic in the space group Pmn2₁-C_2v⁷ with two formulae per unit cell (for data see Inhaltsübersicht). A preparation of pure tetraphenylphosphonium- and -arsoniumhydrogenthiotungstate the first known hydrogenthio salts is given. The salts are characterized by means of vibrational and electronic spectrosocopy, molecular weight determination, and X-ray data.     

Über Oxostannate(II). III. K2Sn2O3, Rb2Sn2O3 und Cs2Sn2O3 – ein Vergleich

On Oxostannates(II). III. K₂Sn₂0₃, Rb₂Sn₂0₃, and Cs₂Sn₂O₃ – a Comparison Hitherto unknown Rb₂Sn₂O₃ has been obtained by heating of mixtures of binary oxides [RbO_0.48 + SnO, Rb:Sn = 1.1:1, Al₂O₃?cylinders, Ar] as deep yellow powder or deep yellow single crystals. It is isotypic to K₂Sn₂O₃, R3 m-D with a = 6.086 Å, c = 15.101 Å, Z = 3, d_calc = 4.69, d_obs = 4.64 g X cm^?3. For 260 hkl it is R = 5.2₇% and R_w = 5.0₉% (MoKα, 4-circle diffractometer data). The structure of K₂Sn₂O₃ and Rb₂Sn₂O₃ is compared with that of Cs₂Sn₂O₃. For both types Effektive Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, have been calculated.     

Übergangsmetallchalkogenverbindungen. Darstellung,IR- und Raman-Spektren sowie röntgenographische Untersuchungen von Verbindungen des Typs A3(MeOS3)Cl und A2MeOS3 (A = K,Rb; Me = Mo W)

Transition Metal Chalkogen Compounds. Preparation, I.R. spectra, Raman Spectra, and X-Ray Investigations on Compounds of the Type A₃(MeOS₃)CI and A₂ MeOS₃(A = K, Rb; Me = Mo, W) The preparation, vibrational spectra, and x-ray data of compounds of the type A₃(MeOS₃)Cl and A₂MeOS₃ (A = K, Rb; Me = Mo, W) are reported. K₃(MoOS₃)Cl, K₃(WOS₃)Cl, and Rb₃(WOS₃)Cl are novel salts which can be prepared by passing H₂S through strong alcaline aqueous MoO and WO solutions containing KCl or RbCl. The salts crystallize in space group Pca2₁? C (No. 29) (Z = 4) with discrete MeOS tetrahedrons. The compounds A₂MeOS₃ (A = K, Rb; Ne = Mo, W) which are in part precipitable only by addition of organic solvents crystallize in space group Pnma? D (No. 62) with four formula units per unit cell.     

Methanolothermal Synthesis and Structures of the Quaternary Group 14 – Group 15 Cesium Selenidometalates Cs3AsGeSe5 and Cs4Ge2Se6

Cs₃AsGeSe₅ and Cs₄Ge₂Se₆ can be prepared by methanolothermal reaction of elemental As, Ge and Se with Cs₂CO₃ at 190 °C. The former quaternary phase contains zweier [{AsGeSe₅}^3?] chains consisting of corner‐bridged GeSe₄ tetrahedra and AsSe₃ pyramids and represents the first Ge^IV‐As^III chalcogenidometalate. Cs₄Ge₂Se₆ exhibits discrete [Ge₂Se₆]^4? anions formed by two edge‐sharing GeSe₄ tetrahedra.     

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 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.     

Darstellung und Kristallstruktur der bekannten Zintl‐Phasen Cs3Sb7 und Cs4Sb2

Synthesis and Crystal Structure of the known Zintl Phases Cs₃Sb₇ and Cs₄Sb₂ Cs₃Sb₇ and Cs₄Sb₂ were synthesized from the elements and their crystal structures were determined on the basis of single crystal x‐ray data. Cs₃Sb₇ crystallizes in the monoclinic system with space group P2₁/c (a = 1605.7(1) pm, b = 1571.1(1) pm, c = 2793.9(2) pm, β = 96.300(2)°, Z = 16) and contains anions Sb₇^3–. In the structure of Cs₄Sb₂ (orthorhombic, space group Pnma, a = 1598.5(3) pm, b = 631.9(2) pm, c = 1099.5(2) pm, Z = 4) dumbbells Sb₂^4– are present.     

Cs2(H3O)Pr(CH3COO)6 und Cs2Pr(CH3COO)5: Synthese,Kristallstrukturen und Thermolyse. Über die analogen Acetate mit Lanthan bis Terbium

Cs₂(H₃O)Pr(CH₃COO)₆ and Cs₂Pr(CH₃COO)₅: Synthesis, Crystal Structures and Thermolysis. Analogous Acetates with Lanthanum through Terbium Single crystals of Cs₂(H₃O)Pr(CH₃COO)₆ are obtained as green plates from an acetic acid solution (≈50%) of Cs₂CO₃ and Pr(CH₃COO)₃ · 1,5 H₂O. The crystal structure monoclinic, Cm, Z = 2, a = 1 540.4(4), b = 691.3(2), c = 1 221.5(4) pm, β = 104.60(5)°, V_m = 379.1(2) cm³/mol, R = 0.040, R_w = 0.035 was determined from four-circle-diffractometer data. The structure consists of monomeric Pr(CH₃COO)₃ units, in which Pr³⁺ is surrounded by nine oxygen atoms. These monomers are linked together to infinite layers parallel (001) by common acetate oxygen atoms with two ?molecules”? of Cs(CH₃COO). Together with an additional acetate ion coordinated to one of the Cs⁺ ions the composition of the layers is [Cs₂Pr(CH₃COO)₆]^?. Between these layers H₃O⁺ is located for electroneutrality. Thermal decomposition of Cs₂(H₃O)Pr(CH₃COO)₆ was examined with thermoanalytical methods (TG/DTA with coupled gas analysis), Guinier-Simon technique and IR spectroscopy: beginning at 70°C the compound looses water and acetic acid. It decomposes topotactically to Cs₂Pr(CH₃COO)₅. At 270°C this acetate decomposes to Cs₂CO₃ and Pr₂O₂CO₃ which emits CO₂ at 600°C form ing Pr₂O₃or PrO_2?x Single crystals of Cs₂Pr(CH₃COO)₅ were obtained from Pr(CH₃COO)₃, in molten Cs(CH₃COO) at about 200°C. The crystal structure tetragonal, P4₃, Z = 4, a = 1 174,5(2), c = 1 480,5(3) pm, V_m = pin,307,5(1) cm³/mol, R = 0,061, R_w= 0,031 again consists of Pr(CH₃COO)₃, monomers where Pr³⁺ has 9 oxygen ligands in its first coordination sphere. They are linked together by two ”molecules“ of cesium acetate to infinite chains along [00l] around the 4, screw axis. There are also acetate bridges between these chains. Isotypic compounds Cs₂(H₃O)M(CH₃COO)₆ and Cs₂M(CH₃COO)₅, and Cs₂M(CH₃COO)₅with M = La? Tb, were obtained from acetic acid solutions or thermal decomposition and were characterized by X-ray Guinier techniques.     

Polychalcogenoaurates(I) with pseudo-onedimensional structures: Preparation and crystal structure of Cs2Au2Se3

Cs₂Au₂Se₃ was obtained as red platelike crystals by reacting a stoichiometric mixture of Cs₂Se, Au and Se at 670K. It crystallizes in space group C2/c, Z = 4 with a = 9.769(5) Å, b = 13.44(1) Å, c = 7.178(3) Å, β = 90.69(1)°. The crystal structure was determined from single crystal data and refined to a conventional R of 0.042 for 674 Fo's and 34 variables. The characteristic structural feature of this new selenoaurate is the formation of infinite helical anionic chains, _∞¹-[AuSeAuSe₂]²⁻ which run parallel to [001] and are separated by the alkali cations. The average Au-Se bond length is 2.402 Å, the bond length in the Se₂-unit is 2.436 Å. Au…Au contacts of 3.200 Å, are formed within the anionic chains. The cesium atoms are coordinated to seven Se in an irregular configuration.     

Tetragonale Fluorperowskite AM0,75 ▭ 0,25F3 mit Kationendefizit: K4MnIIMn2IIIF12 und Ba2Cs2Cu3F12

Tetragonal Fluoroperovskites AM_0,75 □ _0,25F₃ Deficient in Cations: K₄Mn^IIM₂^IIIF₁₂ and Ba₂Cs₂Cu₃F₁₂ By heating 2KMnF₃ + K₂MnF₆ and BaF₂, CsF + CuF₂ respectively, the isostructural tetragonal compounds K₄Mn₃F₁₂ (a = 832.2, c = 1643.0 pm) and Ba₂Cs₂Cu₃F₁₂ (a = 854.1, c = 1704.1 pm) were prepared. They crystallize in a cation-deficient perovskite structure exhibiting ordering of octahedral vacancies. Single crystal structures determinations in the space group I4₁/amd, Z = 4, yielded the following average distances within the octahedra, which are Jahn-Teller distorted for Mn^III and Cu^II:Mn^II? F = 208.3 pm, Mn^III? F = 4 × 183.0/2 × 209.7 pm; Cu? F = 190.7/227.1 and 190.6/236.4 pm, respectively. The results are discussed in comparison with related compounds.     

Über Chalkogenocarbonate. XLVIII. Untersuchungen über die lonen CS2Se2− und CSSe und über Kohlenstoffsulfid-hydrogensulfid-hydrogenselenid SC(SH)(SeH)

CS₂ forms with BaSe in aqueous solution the compound BaCS₂Se. The reaction of CSe₂ with BaS leads to mixed crystals of BaCSSe_a and BaCSe₃. The compounds were investigated by chemical, X-ray and IR-spectroscopical methods. Assignments of all normal vibrations of the ions CS₂Se^2- and CSSe were possible. The conductivity of CS₂Se^2- in aqueous solution was determine. By interaction of BaCS²Se with HCl the acid H₂CS₂SE (red oil) was prepared in form of its S, Se-protonated isomer; fast decomposition to H₂ Se and CS₂ occurs. From conductivity measurements it is concluded that the decomposition of H₂CS₂Se in aqueous solution is a first-order reaction via the anion HCS₂Se^?. Half-lifes and activation energy are given. The dissociation constants K_a1 and K_a2 were determind and thermodynamic data of the dissociation calculate. Date see ?Inhaltsübersicht”?.