Darstellung,Struktur und magnetisches Verhalten von Alkali-metallmanganchalkogeniden A6MnX4 mit A Na oder K und X S,Se oder Te

Inhaltsübersicht. Die Verbindungen Na₆MnS₄, Na₆MnSe₄, Na₆MnTe₄, K₆MnS₄, K₆MnSe₄ und K₆MnTe₄ wurden durch Umsetzungen von Alkalimetallcarbonaten mit Chalkogen und Mangan bzw. Mangancarbonat in einem mit Chalkogen beladenen Wasserstoffstrom erhalten. Röntgenstrukturuntersuchungen an Einkristallen ergaben, daß alle sechs Verbindungen isotyp kristallisieren (Na₆ZnO₄-Typ, Raumgruppe P6₃mc). Als charakteristische Baugruppen treten “isolierte” tetraedrische [MnX₄]-Einheiten auf. Die Temperaturabhängigkeiten der magnetischen Suszeptibilitäten führen zu einem Curie-WeissVerhalten. Erst bei tiefen Temperaturen treten offensichtlich antiferromagnetische Kopplungen auf. Dabei sind die Wechselwirkungen in den Tellurverbindungen stärker als in den Schwefelverbindungen und in den Kaliumverbindungen stärker als in den Natriumverbindungen ausgeprägt. Synthesis, Structure, and Magnetic Properties of Alkali Metal Manganese Chalcogenides A₆MnX₄ with A Na or K and X S, Se or Te The compounds Na₆MnS₄, Na₆MnSe₄, Na₆MnTe₄, K₆MnS₄, K₆MnSe₄ and K₆MnTe₄ were synthesized by the reaction of alkali metal carbonates with chalcogen and Mn or MnCO₃ in a stream of hydrogen charged with chalcogen. Structural investigations on single crystals show that all six compounds crystallize in isotypic atomic arrangements (Na₆ZnO₄-type, space group P6₃mc), which are characterized by isolated [MnX₄] tetrahedra. The magnetic susceptibilities show Curie-Weiss behaviour. At low temperatures there are obviously antiferromagnetic interactions increasing from the sulfides to the tellurides and from the sodium compounds to the potassium compounds.     

Synthesis,Crystal Structures,and Optical Properties of New Quaternary Metal Chalcogenides of Group 5: Cs2AgVS4, K2AgVSe4, Rb2AgVSe4, Rb2AgNbS4, and Cs2AgNbSe4

The new quaternary compounds Cs₂AgVS₄, K₂AgVSe₄, Rb₂AgVSe₄, Rb₂AgNbS₄, and Cs₂AgNbSe₄ were prepared using the reactive flux method. In this structure type infinite chains of edge-sharing AgQ₄- and M^VQ₄-tetrahedra are running parallel to the crystallographic a-axis. The chains are separated by alkali cations. A linear relationship between the size of the alkali cation A⁺ and the Q–Q interchain distances was found. These compounds are isostructural with the analogous quaternary copper chalcogenides. The optical properties were studied by collecting UV/Vis transmission and reflectance spectra which allowed to derive the optical band gaps. The colours of the vanadium compounds range from black to dark violet with optical band gaps between 1.7 and 1.8 eV. In addition, the behaviour of the samples was studied using polarized light. Under these experimental conditions the niobium compound Rb₂AgNbS₄ changes its colour from green to red when the direction of the polarization plane is changed by 90°.     

Alkalimanganselenide und -telluride A2Mn3X4 – Synthese,Kristall- und Spinstruktur

Alkali Metal Manganese Selenides and Tellurides – Synthesis, Crystal and Spin Structures The compounds Rb₂Mn₃Se₄, Cs₂Mn₃Se₄, Rb₂Mn₃Te₄ and Cs₂Mn₃Te₄ were synthesized by the reaction of alkali metal carbonates with chalcogen and Mn or MnCO₃ in a stream of hydrogen charged with chalcogen. Structural investigations show that all compounds crystallize in isotypic atomic arrangements (Cs₂Mn₃S₄-type, space group Ibam, Z = 4). Additionally neutron diffraction experiments were carried out and yielded the spin structures of Rb₂Mn₃Se₄ and Cs₂Mn₃Se₄ (Shubnikov space group Ibam'). The structural related selenides ALiMnSe₂ and ALiZnSe₂ (A = K, Rb or Cs) were synthesized by analogous reactions. All these compounds are isotypic and crystallize in the BaZn₂P₂-structure type.     

Neue Oxozincate der Alkalimetalle: Rb2[ZnO2] und Cs2[ZnO2]

New Oxozineates of Alkali Metals: Rb₂[ZnO₂] and Cs₂[ZnO₂] Colorless single crystals of the hitherto unknown Rb₂[ZnO₂] (a = 9.55₈, b = 6.33₅, c = 15.91 Å, β = 118.6°, z = 8, d_pyk = 4.11, d_rö = 4.21 g · cm^?3) and Cs₂[ZnO₂] (a = 9.85₁, b = 6.61₉, c = 16.26 Å, β = 116.8°) have been prepared, which crystallize monoclinic, P2₁/c – D. (For parameters see text.) Unexpected there are “isolated” groups [Zn₄O₈]. Half of the Zn atoms exhibit the unusual coordination number 3 towards O^2?. The Madelung Part of Lattice Energy, MAPLE, and the Effective Coordination Number, ECoN, the latter by means of Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Tetrahedral [Tt4]4– Zintl Anions Through Solution Chemistry: Syntheses and Crystal Structures of the Ammoniates Rb4Sn4·2NH3, Cs4Sn4·2NH3, and Rb4Pb4·2NH3

The crystalline isotypic solvates Rb₄Sn₄·2NH₃, Cs₄Sn₄·2NH₃, and Rb₄Pb₄·2NH₃ have been synthesized using the direct reduction of elemental tin or tetraphenyltin, respectively, with heavier alkali metals or the dissolution of the binary phase RbPb in liquid ammonia. These compounds contain the cluster ions [Sn₄]^4– or [Pb₄]^4– respectively. This is the first time that[Tt₄]^4– ions (Tt = tetrels) are detected as result of a solution reaction. The accommodation of the ammonia molecules, which build up ion‐dipole interactions to alkali metal cations, requires some modifications of the crystal structures compared to the binary phases RbSn, CsSn, and RbPb. The tetrahedral [Tt₄]^4– anions have a slightly lower coordination by Rb⁺ or Cs⁺ cations and, furthermore, the intercluster distances show a remarkable increase.     

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.     

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.     

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.     

Hochdrucksynthese und Struktur von Rb2PtH6 und Cs2PtH6, ternären Hydriden mit K2PtCl6-Struktur

High-pressure Synthesis and Structure of Rb₂PtH₆ and Cs₂PtH₆, Ternary Hydrides with K₂PtCl₆-Structure The ternary platinum hydrides Rb₂PtH₆ and Cs₂PtH₆ were synthesized by the reaction of rubidium hydride and cesium hydride, respectively, with platinum sponge under a hydrogen pressure above 1 500 bar at 500°C. X-ray investigations on powdered samples and elastic neutron diffraction experiments on the deuterated compounds at the time-of-flight spectrometer POLARIS led to their complete structure determination. Their atomic arrangements are isotypic with that of K₂PtCl₆ containing isolated [PtH₆]^2?-octahedra (space group: Fm3 m, Z = 4).     

Novel Methods of Synthesis of Dibenzo[3n]crown-n and Their Cation Binding Studied by Fluorescence Spectroscopy. Part V

The dibenzo[3n]crown-n were synthesised starting from bis[2-(o-hydroxyphenoxy)ethyl]ether obtained from bis[2-(o-formylphenoxy)ethyl]ether via Baeyer-Villiger oxidation in H₂O₂/CH₃COOH in a good yield. The cyclic condensation ofbis[2-(o-hydroxyphenoxy)ethyl]etherwith tri- and tetraethylene glycol bisdichlorides andthe bisditosylate of pentaethylene glycol in DMF/Me₂CO₃ afforded the large cyclic ethers of dibenzo[21]crown-7, dibenzo[24]crown-8 and dibenzo[27]crown-9. The structures were analysed with IR, ¹H NMR, ¹³C NMR and low-resolution mass spectroscopy methods. The Na⁺, K⁺, Rb⁺ and Cs⁺ cations' recognition of the molecules were conducted withsteady-state fluorescence spectroscopy. The 1:1 association constants, K_a, in acetonitrile were estimated. Dibenzo[21]crown-7 was the best both for K⁺ and Rb⁺ binding but showed too small an effect on Cs⁺. Dibenzo[24]crown-8 exhibited the binding power in the order of Rb⁺ > K⁺ > Na⁺ > Cs⁺. However, dibenzo[27]crown-9 displayed marked binding with only K⁺ but not with Rb⁺ or with Cs⁺ cations probably due to the heavy atom effect of fluorescence quenching.     

Ternäre Halogenide der Seltenen Erden vom Typ A2MX5 (A = K,In, NH4, Rb,Cs; X = Cl,Br, I)

Ternary Rare-Earth Halides of the A₂MX₅ Type (A = K, In, NH₄, Rb, Cs; X = Cl, Br, I) Ternary rare-earth (=M) chlorides, bromides, and iodides In₂MCl₅, (NH₄)₂MCl₅, Rb₂MCl₅, Cs₂MCl₅, CsRbMCl₅, K₂MBr₅, Rb₂MBr₅, K₂MI₅, and Rb₂MI₅ have been synthesized. Single crystals of In₂PrCl₅, Rb₂PrCl₅, K₂PrBr₅, and K₂PrI₅ were grown and the structures refined. The other halides were characterized by x-ray powder patterns. They are isotypic either with K₂PrCl₅(orthorhombic, Pnma, Z = 4, hexagonal arrangement of chains of edge-connected polyhedra [PrX₇]) or with Cs₂DyCl₅ (orthorhombic, Pbnm, Z = 4, hexagonal arrangement of cis-corner-connected octahedra [DyCl₆]) which may be discriminated in structure field diagrams. The thermal expansion was investigated für Cs₂LuCl₅ and Rb₂PrX₅ (X = Cl, Br, I).     

Lösungskalorimetrische Messungen an Doppelchloriden und -bromiden des zweiwertigen Mangans

Thermochemical Data for Manganese(II) Double Chlorides and Bromides by Solution Calorimetry Enthalpies for the reaction nAX + MnX₂ = A_nMnX_(n+2) were determined for all double chlorides and bromides (A ? Na? Cs) existing at 25°C via solution calorimetry. The results are similar to those found for double halides of Mg. Differences between chlorides and bromides are small. The phase diagrams of the systems NaCl/MnCl₂, RbBr/MnBr₂, and CsBr/MnBr₂ were re-investigated by DTA. The structures of the compounds Rb₄MnBr₆, Rb₃MnBr₅; H? Rb₂MnBr₄, and Cs₃MnBr₅ were determined by indexing powder patterns.     

Tricaesium tris(oxalato‐κ2O1,O2)chromate(III) dihydrate

The title compound, Cs₃[Cr(C₂O₄)₃]·2H₂O, has been synthesized for the first time and the spatial arrangement of the cations and anions is compared with those of the other members of the alkali metal series. The structure is built up of alternating layers of either the d or l enantiomers of [Cr(oxalate)₃]³⁻. Of note is that the distribution of the [Cr(oxalate)₃]³⁻ enantiomers in the Li⁺, K⁺ and Rb⁺ tris(oxalato)chromates differs from those of the Na⁺ and Cs⁺ tris(oxalato)chromates, and also differs within the corresponding BEDT‐TTF [bis(ethylenedithio)tetrathiafulvalene] conducting salts. The use of tris(oxalato)chromate anions in the crystal engineering of BEDT‐TTF salts is discussed, wherein the salts can be paramagnetic superconductors, semiconductors or metallic proton conductors, depending on whether the counter‐cation is NH₄⁺, H₃O⁺, Li⁺, Na⁺, K⁺, Rb⁺ or Cs⁺. These materials can also be superconducting or semiconducting, depending on the spatial distribution of the d and l enantiomers of [Cr(oxalate)₃]³⁻.     

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.     

Trennungen von Kationen in Titanhexacyanoferrat(II)-S?ulen

Zusammenfassung Die Trennung der Ionenpaare Rb⁺/Cs⁺, K⁺/Rb⁺, K⁺/Cs⁺, Na⁺/K⁺, Li⁺/Na⁺ mit Salzsäure oder Ammoniumchloridlösung als Elutionsmittel gelingt quantitativ oder nahezu quantitativ mit Hilfe von Titanhexacyanoferrat(II)-säulen. Die Cäsiumionen können nicht eluiert werden. Ebenso gelingt die Trennung der lonenpaare Sr²⁺/Ba²⁺, Ca²⁺/Ba²⁺, Ba²⁺/Cs⁺ und Sr²⁺/Cs⁺ quantitativ oder nahezu quantitativ. Auch eine partielle Trennung der Seltenen Erden ist möglich; Yttrium ist leichter eluierbar als die Lanthanide.

---

Summary The quantitative or nearly quantitative separation of the ion pairs Rb⁺/Cs⁺, K⁺/Rb⁺, k⁺/Cs⁺, Na⁺/K⁺ and Li⁺/Na⁺ can be achieved with hydrochloric acid or ammonium chloride solutions as eluents by means of columns of titanium hexacyanoferrate(II). The elution of the Cs⁺ ions is not possible. In the same way the quantitative or nearly quantitative separation of the ion pairs Sr²⁺/Ba²⁺, Ca²⁺/Ba²⁺, Ba²⁺/Cs⁺ and Sr²⁺/Cs⁺ can be achieved. Also a partial separation of the rare-earth elements is possible; yttrium is more easily eluted than the lanthanides.

     

Röntgenographische Untersuchungen in den Systemen GeO2-{K2O,Rb2O,Cs2O}

Zusammenfassung Folgende GeO₂-reiche Alkaligermanate wurden aufgefunden und röntgenographisch hinsichtlich der Gitterparameter charakterisiert: K₂Ge₈O₁₇ und Rb₂Ge₈O₁₇ (isotyp), Rb₂Ge₇O₁₅ und Cs₂Ge₅O₁₁. Die Existenz der seinerzeit als Pentagermanate beschriebenen isotypen Verbindungen von K, Rb, Cs und Tl sowie deren Gitterparameter werden bestätigt, doch ergab eine ausführliche Prüfung an gut kristallisierten Produkten zusammen mit den genau bestimmten Dichtewerten eine geringfügige Verschiebung im Verhältnis Me₂O/GeO₂, entsprechend einer Formel Me₂Ge₆O₁₃.

---

The GeO₂-rich regions of alkaline germanate systems have been examined by X-rays. The compounds K₂Ge₈O₁₇ and Rb₂Ge₈O₁₇ (isostructural), Rb₂Ge₇O₁₅ and Cs₂Ge₅O₁₁ have been detected and characterized by their lattice parameters. The existence as well as the cell dimensions of the isotypic compounds previously described as pentagermanates have been corroborated; a detailed investigation of completely crystallized material gives strong evidence for a lower Me₂O/GeO₂-ratio, in accordance with precise density measurements. Thus a formulaMe ₂Ge₆O₁₃ (Me=K, Rb, Cs, Tl) has to be assumed.

     

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.     

Study of the paramagnetic centers in heterofullerides MnM′3-nC60 (M = K, Rb, Cs; M′ = Be, Mg, Ca, Ba; n = 1, 2)

New heterofullerides Cs₂MC₆₀, CsM₂C₆₀, Rb₂MC₆₀, K₂MC₆₀, and KM₂C₆₀ (M = Be, Mg, Ca, Ba) have been synthesized; the temperature dependences of the magnetic susceptibilities of these compounds in the temperature range from 4.2 to 297 K have been measured. Among these heterofullerides, K₂MgC₆₀, KMg₂C₆₀, K₂CaC₆₀, K₂BeC₆₀, and Rb₂BeC₆₀ pass to the superconducting state at temperatures T _c = 13–24.3 K. The paramagnetic electronic states of the compounds have been studied by EPR at temperatures of 105–300 K, which shows the existence of two types of paramagnetic centers, related to oxygen defects and conduction electrons.     

Enthalpy of Phase Transitions and Heat Capacity of Stoichiometric Compounds in LaBr3-MBr Systems (M=K,Rb, Cs)

Molar enthalpies of solid-solid and solid-liquid phase transitions of the LaBr₃, K₂LaBr₅, Rb₂LaBr₅, Rb₃LaBr₆ and Cs₃LaBr₆ compounds were determined by differential scanning calorimetry. K₂LaBr₅ and Rb₂LaBr₅ exist at ambient temperature and melt congruently at 875 and 864 K, respectively, with corresponding enthalpies of 81.5 and 77.2 kJ mol^-1. Rb₃LaBr₆ and Cs₃LaBr₆ are the only 3:1 compounds existing in the investigated systems. The first one forms from RbBr and Rb₂LaBr₅ at 700 K with an enthalpy of 44.0 kJ mol^-1 and melts congruently at 940 K with an enthalpy of 46.7 kJ mol^-1. The second one exists at room temperature, undergoes a solid-solid phase transition at 725 K with an enthalpy of 9.0 kJ mol^-1 and melts congruently at 1013 K with an enthalpy of 57.6 kJ mol^-1. Two other compounds existing in the CsBr-based systems (Cs₂LaBr₅ and CsLa₂Br₇) decompose peritectically at 765 and 828 K, respectively. The heat capacities of the above compounds in the solid as well as in the liquid phase were determined by differential scanning calorimetry. A special method - 'step method' developed by SETARAM was applied in these measurements. The heat capacity experimental data were fitted by a polynomial temperature dependence. This revised version was published online in July 2006 with corrections to the Cover Date.     

K2NaGaP2, Cs2NaGaP2, K2NaGaAs2, K2NaInP2 und K2NaInAs2, Verbindungen mit den SiS2-isosteren Polyanionen [MX4/2]3− (MGa,In; XP,As)

K₂NaGaP₂, Cs₂NaGaP₂, K₂NaGaAs₂, K₂NaInP₂ and K₂NaInAs₂, Compounds with the Polyanions [MX_4/2]^3? (M?Ga, In; X?P, As) isosteric with SiS₂ The title compounds are synthesized from stoichiometric mixtures of the elements or from Na, KP(KAs), Cs₄P₆ and MX (M?Ga, In; X?P, As) at 950K. They are isotypic and crystallize in the space group Ibam (No. 72) with Z=4. The anionic partial structure is characterized by infinite chains [MX_4/2]^3? which are isosteric to SiS₂. Vibrational spectra are measured and interpreted based on the symmetry D_4h-P(2/m 2/c)4₂/m of the isolated polymer chain [MX₂]^3?. A good agreement between observed and calculated frequencies is obtained by using a force field of the tetrameric fragment [M₄X₁₀]^18? (three four-membered M₂X₂ rings).