Schwingungsspektren der Bis(mercuriojodonium)-hexafluorometallate (HgJ)2MF6 (M = Ti,Zr, Sn) und verwandter Verbindungen

Vibrational Spectra of Bis (mercurioiodonium)-hexafluorometallates (HgI)₂ MF₆(M = Ti, Zr, Sn) and Similar Compounds For the isotypic bis(mercurioiodonium)-hexafluorometallates (HgI)₂MF₆ (M = Ti, Zr and Sn; space group D–Cmcm) with chain structure of the cations [(IHg_2/2)₂]²⁺ the complete vibrational spectra have been discussed on the basis of a factor group analysis. A simple model yields an average force constant f ? 1.37 N · cm^?1 for the Hg? I bonds of the chains and bond angles at the iodine atoms which agree satisfactorily with the data obtained by X-ray structure analysis. Spectra of (HgI)X (X = NO₃ and BF₄; benzene sulphonate and p-toluene sulphonate) also indicate cationic chains in these compounds.     

Zur Kenntnis der inversen Perowskite M3TO (M = Ca,Sr, Yb; T = Si,Ge, Sn,Pb)

On the Inverse Perovskites M₃TO (M = Ca, Sr, Yb; T = Si, Ge, Sn, Pb) Ca₃SiO and seven further inverse perovskites M₃TO (M = Ca, Sr, Yb; T = Si, Ge, Sn, Pb) were prepared in iron crucibles under argon by the reactions 6 M + TO₂ + T = 2 M₃TO, and 3 M+ TO = M₃TO for Yb₃PbO, respectively, at temperatures between 1123 to 1173 K. The crystal structures of all compounds were solved and refined using X—ray powder diffraction methods. Ca₃SiO, Ca₃GeO, Sr₃SiO, Sr₃GeO, Yb₃SiO and Yb₃GeO are orthorhombic perovskites (anti—GdFeO₃—type, space group Pbnm, No. 62, Z = 4). They show slightly distorted corner—sharing OM₆ octahedra that are tilted with respect to their positions in the ideal perovskite structure. The effective radii of the T^4— vary significantly with M²⁺. Thus, these perovskites can no longer be discussed in terms of the hard—sphere model, and Goldschmidt's tolerance factor does not apply. The ideal cubic representatives Yb₃SnO and Yb₃PbO were refined in space group Pm3¯m (anti—SrTiO₃ type, Z = 1).     

Zur Kenntnis der RbNiCrF6Typs. III. Neue Fluoride des Typs CsZnMF6 mit M = Al,Ga, In,Tl, Sc,Ti, V,Mn, Cu,Rh

On the RbNiCrF₆ Type. III. New Fluorides of the Type CsZnMF₆ (M = Al, Ga, In, Tl, Sc, Ti, V, Mn, Cu, Rh) Cubic compounds are CsZnGaF₆ [3] (colourless, a = 10.29 Å); CsZnInF₆ (colourless, a = 10.58 Å); CsZnTlF₆ (colourless, a = 10.62 Å); CsZnScF₆ (colourless, a = 10.58 Å); CsZnTiF₆ (lightblue, a = 10.50 Å); CsZnVF₆ (lightgreen, a = 10.43 Å); CsZnMnF₆ (redbrown, a = 10.40 Å); CsZnCuF₆ (light brown, a = 10.24 Å); CsZnRhF₆ (redbrown, a = 10.41 Å), all RbNiCrF₆ type of structure, in addition non cubic: CsZnAlF₆ (colourless). The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Ag2+ in trigonal-bipyramidaler Umgebung: Neue Fluoride mit zweiwertigem Silber: AgMMF20 (MII = Cd,Ca, Hg; MIV = Zr,Hf)

Ag²⁺ in Trigonal-Bipyramidal Surrounding New Fluorides with Divalent Silver AgM M F₂₀ (M^II = Cd, Ca, Hg; M^IV = Zr, Hf) The intensively green compounds AgMMMF₂₀ (M^II = Cd, Ca, Hg; M^IV = Zr, Hf) have been obtained for the first time as single crystals and investigated by X-ray methods. They crystallize in space group P6₃/m-C_6h² (Nr. 176) with

• a = 1052.0(2) pm, c = 828.6(2) pm (AgCd₃Zr₃F₂₀),
• a = 1048.0(2) pm, c = 832.6(3) pm (AgCd₃Hf₃F₂₀),
• a = 1059.4(2) pm, c = 841.0(3) pm (AgCa₃Zr₃F₂₀),
• a = 1053.7(2) pm, c = 830.6(3) pm (AgCa₃Hf₃F₂₀),
• a = 1058.9(3) pm, c = 832.6(4) pm (AgHg₃Zr₃F₂₀),
• a = 1056.9(2) pm, c = 833.0(3) pm (AgHg₃Hf₃F₂₀), Z = 2.

     

Zur Struktur der LiMIIMIIIF6-Verbindungen. Neue Verbindungen mit MIII=In und Ti

On the Structure of LiM^IIM^IIIF₆ Compounds. New Compounds with M^III=IN and Ti LiMn^IIInF₆ compounds with M^II = Mg, Mn, Co, Ni, Zn, Cd and Ca crystallize in the Na₂SiF₆ structure. The Ti(III) compound LiMgTiF₆ has trirutile structure, LiMnTiF₆ has Na₂SiF₆ and trirutile structure (H.-T. modification), LiCaTiF₆ and LiCdTiF₆ have Li₂ZrF₆ superstructure. With M^II = Co, Ni and Zn solid solutions trirutile — MF₂(rutile) could be only prepared. The lattice constants of all compounds are reported. For LiMnVF₆ and LiFeGaF₆ too dimorphism Na₂SiF₆ trirutile was observed. In the system LiNiCrF₆ (trirutile) — LiMnCrF₆ (Na₂SiF₆ structure) phase limits of both structures are determined in dependence on the ratio of ionic radii r/r. Magnetic data of the In compounds with M^II = Co and Ni and of the Ti(III) compounds with M^II = Mg, Zn, Mn, just as of α- and β-LiMnVF₆ are also given. The three structures only exist if r reaches from 0.6 to 1.2 Å and r from 0.5 to 0.8 Å. The stability-fields are determined by the ratio of ionic radii r/r_Li, r/r_Li and r/r: trirutile 0.9–1.2, Na₂SiF₆ type 1.2–～1.4 and Li₂ZrF₆ superstructure >1.4. The dependence of rate of ionic radii is explained by the different sharing of MF₆ octahedra.     

Zur Kenntnis des RbNiCrF6-Typs. V. Neue Fluoride CsBMF6 mit B = MnII bzw. NiII und M = Ga,Fe, Rh bzw. Sc,In, Tl,Rh

On the RbNiCrF₆ Type. V. New Fluorides of the Type CsBMF₆ with B = Mn^II or Ni^II and M = Ga, Fe, Rh or Sc, In, Tl, Rh New prepared are the cubic compounds CsNiScF₆ (light yellow, a = 10.60 Å); CsNiInF₆ (lightyellow, a = 10.64 Å); CsNiTlF₆ (light yellow, a = 10.60 Å); CsNiRhF₆ (light redbrown, a = 10.37 Å); CsMnGaF₆ (pink, a = 10.42 Å); CsMnFeF₆ (light green, a = 10.55 Å) and CsMnRhF₆ (redbrown, a = 10.58 Å), all RbNiCrF₆ type of structure. The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Neue Fluoride MIIIMIVF7 mit MIII = SE,Tl und MIV = Sn,Pb, Pt

New Fluorides M^IIIM^IVF₇ with M^III = SE, Tl and M^IV = Sn, Pb, Pt Colourless Fluorides MSnF₇ (M = La, Sm, Gd, Yb, Lu, Tl), TlPbF₇ and yellow compounds MPtF₇ (M = Eu, Y, Lu) were obtained for the first time either as single crystals or powder samples. They crystallize isostructural to SmZrF₇ (space group P2₁/c-C_2h⁵, Nr. 14; P2₁/n, Z = 4). Crystal data see “Inhaltsübersicht”.     

Zur Kenntnis des RbNiCrF6-Typs,IV. Neue Fluoride des Typs CsPdMF6 mit M = Al,Ga, In und Sc,Fe, Mo,Rh

On the RbNiCrF₆ Type. IV. New Fluorides of the Type CsPdMF₆ (M = Al, Ga, Sc, In, Fe, Rh, Mo) New prepared are the cubic compounds CsPdScF₆ (brown violet, a = 10.82 Å); CsPdInF₆ (brown violet, a = 10.89); CsPdFeF₆ (redbrown, a = 10.64 Å); CsPdRhF₆ (redbrown, a = 10.65 Å), all of RbNiCrF₆-Type of structure. In addition prepared are CsPdAlF₆ (light violet, non cubic) CsPdGaF₆ (violet, non cubic) and CaPdMoF₅ (redbrown, non cubic). The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Preparation and crystal data of the New Pyrochlores Pb2[M1.5Te0.5]O6.5 (M = Ti,Zr, Sn,Hf)

From mixtures of PbO, MO₂ (M = Ti, Zr, Hf), SnO, and TeO₂, four new oxides Pb₂[M_1.5Te_0.5]O_6.5 have been obtained as yellow powders giving X-ray diffraction patterns characteristic of cubic pyrochlores, S.G. Fd3 m (No. 227), Z = 8, and a/Å values from 10.3529(1) (M = Ti) to 10.7406(1) (M = Zr). The best R factors, from 0.0465 (M = Ti) to 0.0242 (M = Hf), were obtained for Pb in 16(c) positions, M and Te (3:1) randomly distributed in 16(d), oxygen atoms in 48(f) and in a half of the 8(a) sites, and x values for the oxygen positional parameter (origin at center, 3 m) from 0.436 (M = Ti) to 0.421 (M = Zr). For the compounds of Ti and Zr the angles of the coordination polyhedra around the metals are reported. For seven-coordinated Pb^II the stereochemical influence of the nonbonded electron pair is shown. Apparent interatomic distances agree with those calculated.     

Synthese und Kristallstruktur von Silber(II)‐Fluoriden AgMIVF6 (MIV = Sn,Ti, Pb,Pd, Pt,Rh)

Synthesis and Crystal Structure of Silver(II) Fluorides AgM^IVF₆ (M^IV = Sn, Ti, Pb, Pd, Pt, Rh) For the first time single crystals of AgSnF₆ (light blue, triclinic with a = 519.93(7) pm, b = 524.96(10) pm, c = 563.13(9) pm, α = 115.66(2)°, β = 89.28(2)°, γ = 118.77(2)°, spcgr. P1–C ; (No. 2), Z = 1) and AgPdF₆ (brown green, triclinic with a = 501.5(2) pm, b = 508.7(2) pm, c = 996.4(2) pm, α = 89.58(2)°, β = 103.10(2)°, γ = 120.88(2)°, spcgr. P1–C , (No. 2), Z = 2) have been synthesized and investigated. Other compounds of this type, like AgTiF₆ and AgPbF₆ (isotypic to AgSnF₆) or AgPtF₆ and AgRhF₆ (isotypic to AgPdF₆) have been synthesized in form of microcrystalline powders, their lattice parameters have been determined by Guinier data. All compounds are structure variants oft the LiSbF₆‐type and isotypic with CuMF₆ (M = Ti, Sn, Pb and Pd, Pt, respectively).     

Magnetische Eigenschaften der Verbindungen BaMF4 und Pb2 MF6 (M=Mn,Fe, Co,Ni, Cu,Zn)

Zusammenfassung In den beiden untersuchten Doppelfluorid-Serien, BaMF₄ und Pb₂ MF₆ (M=Mn, Fe, Co, Ni, Cu, Zn), zeigen die Verbindungen des Cu und des Zn ein anderes Verhalten als die übrigen. Die Zn-Verbindungen sind diamagnetisch, die Cu-Verbindungen paramagnetisch. Pb₂CuF₆ befolgt dasCuriesche Gesetz, während BaCuF₄ eineCurie-Weiss-Abweichung unterhalb 212 K aufweist.Im untersuchten Temperaturbereich zeigt sich für alle anderen Verbindungen, mit Ausnahme von Pb₂FeF₆, Antiferromagnetismus.

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Magnetic properties of the compounds BaMF₄ and Pb₂ MF₆ (M=Mn, Fe, Co, Ni, Cu, Zn)

Two series of double fluorides, BaMF₄ and Pb₂ MF₆ (M=Mn, Fe, Co, Ni, Cu, Zn) have been studied, the compounds of Cu and Zn differing in behaviour from the others. The Zn componds are diamagnetic, the Cu compounds paramagnetic. Pb₂CuF₆ conforms toCurie's law while BaCuF₄ exhibits aCurie-Weiss deviation below 212° K.With the exception of Pb₂FeF₆, all the other compounds show antiferromagnetism in the studied temperature range.

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Herrn Prof. Dr.Hans Nowotny ergebenst gewidmet.     

Zur Kenntnis komplexer Fluoride mit Cu2+ und Pd2+: MPtF6 (M  Pd,Cu) und RbCuPdF5

On Complex Fluorides with Cu²⁺ and Pd²⁺: MPtF₆ (M ? Pd, Cu) and RbCuPdF₅ For the first time single crystals of PdPtF₆ (green), trigonal-rhomboedric, a = 503.8, c = 1431.6 pm, spcgr. R3 ? C (No. 148), Z = 3, CuPtF₆ (orange), triclinic, a = 495.2, b = 498.5, c = 962.4 pm, α = 89.98, β = 104.23, γ = 120.35°, spcgr. P1 ? C (No. 2), Z = 2 and RbCuPdF₅ (orange brown, in connection with investigations on M^IPd₂F₅ [1]), orthorhombic, a = 626.9, b = 719.9, c = 1076.3 pm, spcgr. Pnma? D (No. 62), Z = 4, four circle diffractometer data, have been obtained.     

Synthese von [SiW11O39MF]5– (M = Zr,Hf) – den ersten Heteropolyoxowolframaten mit terminal gebundenem Fluor

Synthesis of [SiW₁₁O₃₉MF]^5– (M = Zr, Hf) – the First Heteropolyoxotungstates with Terminal Bonded Fluorine The reaction of metal fluorides of Group 4 with lacunar [α-SiW₁₁O₃₉]^8– resulted in the formation of metal fluorides containing inorganic clusters. In the case of titanium all metal fluorine bonds are cleaved, while the corresponding reaction of zirconium and hafnium, respectively gave compounds having one metal fluorine bond. The new compounds contain an additional active NMR probe.     

Magnetische Messungen anHeusler-Phasen (Co,Mn)2 XY (X=Ti,Zr,Hf und Mn;Y=Ge und Sn)

Magnetic measurements onHeusler alloys (Co,Mn)₂ XY have been performed. With a few exceptions there is no enhancement of ferromagnetism while substituting cobalt by manganese. The results can be explained by a partially antiferromagnetic ordering of the manganese atoms.     

Les phases Na4XO4 (X = Si,Ti, Cr,Mn, Co,Ge, Sn,Pb) et K4XO4 (X = Ti,Cr, Mn,Ge, Zr,Sn, Hf,Pb)

The isotypic Na₄XO₄ (X = Si, Ti, Cr, Mn, Co, Ge, Sn, Pb) and K₄XO₄ (X = Ti, Cr, Mn, Ge, Zr, Sn, Hf, Pb) phases crystallize in the triclinic system. Optical and magnetic properties of the chromium, manganese, and cobalt compounds show that the transition element has a tetrahedral surrounding.     

Präparation und röntgenographische Charakterisierung der Verbindungen Ca3M2Ga2 (M = Pd,Pt) und Ca3M2Ga3 (M = Rh,Ir)

Preparation and Crystal Structures of the Compounds Ca₃Pd₂Ga₂, Ca₃Pt₂Ga₂, Ca₃Rh₂Ga₃, and Ca₃Ir₂Ga₃ The new compounds Ca₃Pd₂Ga₂, Ca₃Pt₂Ga₂, Ca₃Rh₂Ga₃, and Ca₃Ir₂Ga₃ were prepared by heating appropriate mixtures of the elements under an Argon-atmosphere. The results of the structure analysis of single crystals by means of X-ray diffraction are given in the section “Inhaltsübersicht”. Ca₃Pd₂Ga₂ and Ca₃Pt₂Ga₂ are isotypic and form the Y₃Rh₂Si₂ type structure (Pbcm), where the platinium metals have a trigonal environment consisting of Ga-atoms. The isotypic compounds Ca₃Rh₂Ga₃ and Ca₃Ir₂Ga₃ (Pbcm) form a new type of structure, which is related to the Y₃Rh₂Si₂ type with a distorted tetrahedral surrounding of Ga-atoms for Rh (resp. Ir).     

Li mobility in Nasicon-type materials LiM2(PO4)3, M = Ge, Ti, Sn, Zr and Hf, followed by 7Li NMR spectroscopy

Lithium mobility in LiM(2)(PO(4))(3) compounds, M = Ge and Sn, has been investigated by (7)Li Nuclear Magnetic Resonance (NMR) spectroscopy, and deduced information compared with that reported previously in Ti, Zr and Hf members of the series in the temperature range 100-500 K. From the analysis of (7)Li NMR quadrupole interactions (C(Q) and η parameters), spin-spin T(2)(-1) and spin-lattice T(1)(-1) relaxation rates, structural sites occupancy and mobility of lithium have been deduced. Below 250 K, Li ions are preferentially located at M(1) sites in rhombohedral phases, but occupy intermediate M(12) sites between M(1) and M(2) sites in triclinic ones. In high-temperature rhombohedral phases, a superionic state is achieved when residence times at M(1) and M(12) sites become similar and correlation effects on Li motion decrease. This state can be obtained by large order-disorder transformations in rhombohedral phases or by sharp first order transitions in triclinic ones. The presence of two relaxation mechanisms in T(1)(-1) plots of rhombohedral phases has been associated with departures of conductivity from the Arrhenius behavior. Long term mobility of lithium is discussed in terms of the cation vacancy distribution along conduction paths.     

Magnetische Messungen anHeusler-Phasen (Co,Ni)2 XY (X=Ti,Zr, Hf,V und Mn;Y=Ge und Sn)

Magnetic measurements onHeusler alloys (Co, Ni)₂ XY are performed. The transitions from ferromagnetic to paramagnetic behaviour in some systems are of special interest.

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