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 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 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 Kenntnis des RbNiCrF6-Typs: über CsCuMF6 (M  NiIII,TiIII), CsMgMF6 (M  Co,Fe, Ga) und CsZnMF6 (M  NiIII,CoIII, FeIII)

On the RbNiCrF₆ Type(¹): On CsCuMF₆ (M?Ni^III, Ti^III), CsMgMF₆ (M ?Co, Fe, Ga), and CsZnMF₆ (M?Ni^III, Co^III, Fe^III) New prepared are the cubic compounds CsCuNi^IIIF₆ (dark brown, a = 10.14 Å); CsZnNi^IIIF₆ (dark brown, a = 10.17 Å); CsCuTi^IIIF₆ (light grey, a = 10.39 Å); CsMgGaF₆ (colourless, a = 10.23 Å); CsMgFeF₆ (colourless, a = 10.53 Å); CsZnFeF₆ (colourless, a = 10.42 Å); CsMgCo^IIIF₅ (light blue, a = 10.27 Å) and CsZnCo^IIIF₆ (light blue, a = 10.34 Å), all RbNiCrF₆-type of structure. The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Uber Hexafluorotitanate (III). Cs2MTiF6 und Rb2MTiF6 (M  K bzw. Na); mit einer Bemerkung über Tl3TiF6

On Hexafluorotitantes (III). Cs₂MTIF₄ and Rb₂MTIF₄(M?K, Na); with a Remark on TI₃TIF₆ By heating the binary fluorides in a closed system we obtained Cs₂KTiF₆ (a = 9.12₄ Å), Rb₂KTiF₆ (a = 8.93₂ Å) and Rb₂NaTiF₆ (a = 8.53₃ Å), all cubic Elpasolithes of light blue colour as well as Cs₂NaTiF₆ (hexagonal a = 6.27₂, c = 30.91 Å, isotypic with Cs₂NaCrF₆) and Tl₃TiF₆ TiF₃ (3.1–295.5°K) and Cs₂KTiF₆ (74.9–297.7°K) have been measured magnetically. The spectra of reflection in the range of 10 000 to 30 000 cm^?1 of TiF₃ and the new quaternary fluorides are similar. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Zur Kenntnis der Hexafluorocuprate(III)

On Hexafluorocuprates (III) New prepared are: Cs₂LiCuF₆ (green, trigonal isotypic to Cs₂LiGaF₆; a = 621.5, c = 503.3 pm, γ = 120° from CsCuCl₃, CsCl, Li₂CO₃, p_F2 = 1 bar, 350°C, 2w); K₂LiCuF₆ (green, cubic isotypic to K₂NaCrF₆; a = 792.5 pm from KCuCl₃, Li₂CO₃, KCl, p_F2, = 35 bar, 480°C, 3 d); CsRb₂CuF₆ (green, cubic isotypic to inv. K₂NaCrF₆; a =899,6 pm from CsCuCl₃, RbCl, p_F2 = 1 bar, 400°C, 7 d); CsRbKCuF₆ (green, cubic isotypic to K₂NaCuF₆; a = 886.1 pm from KCuCl₃, CsCl, RbCl, p_F2 = 1 bar, 400°C, 7 d); CsCuCuF₆ (black, orthorhombic isotypic to CsNiNiF₆; a = 706.7, b = 727.7, c = 1032.2 pm from CsCuCl₃, CuCl₂ · 2H₂O, p_F2 = 30 bar, 400°C, 20 h); CsBaCuF₆ (green, tetragonal; a = 598.1, c = 864.6 pm from ?BaCuO₂’?, CsCl, p_F2 = 350 bar, 400°C, 7 d). Also prepared: Cs₂RbCuF₆, Cs₂KCuF₆, Cs₂NaCuF₆, Rb₂KCuF₆, Rb₂NaCuF₆, Rb₂LiCuF₆, K₂NaCuF₆, Na₃CuF₆, K₃CuF₆, Rb₃CuF₆, Cs₃CuF₆ and CsZnCuF₆ (parameters see text). The Madelungpart of Lattice Energy, MAPLE are calculated and discussed. All samples are paramagnetic and follow (exception: CsZnCuF₆) the Curie-Weiss-Law.     

Rubidium-decaamidodichromat(III), Rb4Cr2(NH2)10 – Synthese und Kristallstruktur

Rubidium Decaamidodichromate(III), Rb₄Cr₂(NH₂)₁₀ – Synthesis and Crystal Structure The reaction of chromium(III) with rubidium amide in a molar ratio of Cr(NH₂)₃/RbNH₂ = 1 : 1.75 at 140 °C and p(NH₃) = 3 kbar in a high-pressure autoclave results after 90 days in dark violet crystals of Rb₄Cr₂(NH₂)₁₀. Structure determination was done by single crystal X-ray methods:Pna2₁ (No. 33), Z = 4, a = 12.244(3) Å, b = 6.727(1) Å, c = 19.775(5) Å, N(F²_o > 3σ(F²_o)) = 1046, N(Var.) = 94, R/R_w = 0,051/0,059&#TAB;The structure of Rb₄Cr₂(NH₂)₁₀ contains isolated, face-sharing N-octahedra around two Cr³⁺-ions giving [Cr(NH₂)₃(NH₂)_3/2]₂^3–. These are arranged to oneanother following the motif of a hexagonal closest packing. They are connected via Rb⁺- and one further amide ion not bound to Cr³⁺. The compound is characterized by thermoanalytical and IR-/Raman-spectroscopic measurements.     

Drei neue Selenoborato-closo-dodekaborate: Synthesen und Kristallstrukturen von Rb8[B12(BSe3)6], Rb4Hg2[B12(BSe3)6] und Cs4Hg2[B12(BSe3)6]

Three Novel Selenoborato- closo -dodecaborates: Syntheses and Crystal Structures of Rb₈[B₁₂(BSe₃)₆], Rb₄Hg₂[B₁₂(BSe₃)₆], and Cs₄Hg₂[B₁₂(BSe₃)₆] The three selenoborates Rb₈[B₁₂(BSe₃)₆] (P1, a = 10.512(5) Å, b = 10.450(3) Å, c = 10.946(4) Å, α = 104.53(3)°, β = 91.16(3)°, γ = 109.11(3)°, Z = 1), Cs₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.860(2) Å, b = 10.740(2) Å, c = 11.078(2) Å, α = 99.94(3)°, β = 90.81(3)°, γ = 115.97(3)°, Z = 1), and Rb₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.593(2) Å, b = 10.458(2) Å, c = 11.131(2) Å, α = 99.25(3)°, β = 91.16(3)°, γ = 116.30(3)°, Z = 1) were prepared from the metal selenides, amorphous boron and selenium by solid state reactions at 700 °C. These new chalcogenoborates contain B₁₂ icosahedra completely saturated with six trigonal-planar BSe₃ entities functioning as bidentate ligands to form a persubstituted closo-dodecaborate anion. The two isotypic compounds Rb₄Hg₂[B₁₂(BSe₃)₆] and Cs₄Hg₂[B₁₂(BSe₃)₆] are the first selenoborate structures containing a transition metal which are characterized by single crystal diffraction.     

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.     

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.     

Syntheses and Crystal Structures of Rb2B2Se7, Tl2B2Se7, Cs3B3Se10, and Tl3B3Se10: New Perseleno‐selenoborates with Polymeric Anionic Chains

The perseleno‐selenoborates Rb₂B₂Se₇ and Cs₃B₃Se₁₀ were prepared from the metal selenides, amorphous boron and selenium, the thallium perseleno‐selenoborates Tl₂B₂Se₇ and Tl₃B₃Se₁₀ directly from the elements in evacuated carbon coated silica tubes by solid state reactions at temperatures between 920 K and 950 K. All structures were refined from single crystal X‐ray diffraction data. The isotypic perseleno‐selenoborates Rb₂B₂Se₇ and Tl₂B₂Se₇ crystallize in the monoclinic space group I 2/a (No. 15) with lattice parameters a = 12.414(3) Å, b = 7.314(2) Å, c = 14.092(3) Å, β = 107.30(3)°, and Z = 4 for Rb₂B₂Se₇ and a = 11.878(2) Å, b = 7.091(2) Å, c = 13.998(3) Å, β = 108.37(3)° with Z = 4 for Tl₂B₂Se₇. The isotypic perseleno‐selenoborates Cs₃B₃Se₁₀ and Tl₃B₃Se₁₀ crystallize in the triclinic space group P1 (Cs₃B₃Se₁₀: a = 7.583(2) Å, b = 8.464(2) Å, c = 15.276(3) Å, α = 107.03(3)°, β = 89.29(3)°, γ = 101.19(3)°, Z = 2, (non‐conventional setting); Tl₃B₃Se₁₀: a = 7.099(2) Å, b = 8.072(2) Å, c = 14.545(3) Å, α = 105.24(3)°, β = 95.82(3)°, γ = 92.79(3)°, and Z = 2). All crystal structures contain polymeric anionic chains of composition ([B₂Se₇]^2–)_n or ([B₃Se₁₀]^3–)_n formed by spirocyclically fused non‐planar five‐membered B₂Se₃ rings and six‐membered B₂Se₄ rings in a molar ratio of 1 : 1 or 2 : 1, respectively. All boron atoms have tetrahedral coordination with corner‐sharing BSe₄ tetrahedra additionally connected via Se–Se bridges. The cations are situated between three polymeric anionic chains leading to a nine‐fold coordination of the rubidium and thallium cations by selenium in M₂B₂Se₇ (M = Rb, Tl). Coordination numbers of Cs⁺ (Tl⁺) in Cs₃B₃Se₁₀ (Tl₃B₃Se₁₀) are 12(11) and 11(9).     

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.     

Na2B2Se7, K2B2S7 und K2B2Se7: Drei Perchalkogenoborate mit neuem polymeren Anionengerüst

Na₂B₂Se₇, K₂B₂S₇, and K₂B₂Se₇: Three Perchalcogenoborates with a Novel Polymeric Anion Network Na₂B₂Se₇ (I 2/a; a = 11.863(4) Å, b = 6.703(2) Å, c = 13.811(6) Å, β = 109.41(2)°; Z = 4), K₂B₂S₇ (I 2/a; a = 11.660(2) Å, β = 6.827(1) Å, c = 12.992(3) Å, β = 106.78(3)°; Z = 4), and K₂B₂Se₇ (I 2/a; a = 12.092(4) Å, b = 7.054(2) Å, c = 13.991(5) Å, β = 107.79(3)°; Z = 4) were prepared by reaction of stoichiometric amounts of sodium selenide (potassium sulfide) with boron and sulfur or of potassium selenide and boron diselenide, respectively, at 600°C with subsequent annealing. The crystal structures consist of polymeric anion chains of composition ([B₂S₇]^2?)_n or ([B₂Se₇]^2?)_n formed by spirocyclically connected five-membered B₂S₃ (B₂Se₃) rings and six-membered B₂S₄ (B₂Se₄) rings. The nine-coordinate alkaline metal cations are situated in between.     

Die Kristallstruktur von Cs2NaInF6

Using single crystal data the occurence of the K₂NaCrF₆ type of structure for Cs₂NaInF₆ (a = 8.905 Å) has been confirmed and x_F determined to be x_F = 0.229; in consequence: In–F = 2.03₉ Å [430 (hkl) with h + k = 2n and h = 0 to 7; R = 11.1%; Mo? K_α.]. The Madelung Part of Lattice Energy is calculated and discussed in detail.     

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.     

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).     

Zur kristallchemischen Ähnlichkeit von Aurid- und Halogenid-Ionen

On the Crystal Chemical Similarity of Auride and Halide Anions The crystallographic properties of the aurides M₃AuO and the alkalimetal halide oxides M₃XO (M = K, Rb, Cs; × = Br, I) are compared. Rb₃BrO, Rb₃IO, Cs₃BrO, and Cs₃IO have been prepared and characterized for the first time: Rb₃BrO (a = 5.465(1) Å) crystallizes as a cubic anti perovskite, Cs₃BrO (a = 7.800(6), c = 7.122(6) Å) and Cs₃IO (a = 8.056(3), c = 7.168(3) Å) as hexagonal anti perovskites, Rb₃IO (a = 7.889(1), c = 19.640(1) Å) as a hexagonal anti BaTiO₃ type. The analysis of bond lengths, molar volumes and the systematic of the crystal structures leeds to the conclusion, that the crystallographic properties of auride- and bromide anions are similar. The radius of the Au^? has been found to be 2.2 Å (KZ 12).     

Zur Kenntnis der Hexafluororhodate(III): Über Cs2K[RhF6], Rb2K[RhF6], K2Na[RhF6], Rb2Na[RhF6] und Tl2Na[RhF6]

On the Knowledge of Hexafluororhodates(III): Cs₂K[RhF₆], Rb₂K[RhF₆], K₂Na[RhF₆], Rb₂Na[RhF₆] and Tl₂Na[RhF₆]. New prepared are the compounds Cs₂KRhF₆ (a = 9.04₉ Å), Rb₂NaRhF₆ (a = 8.49₂ Å), Rb₂KRhF₆ (a = 8.87₆ Å), K₂NaRhF₆ (a = 8.36₂ Å) and Tl₂NaRhF₆ (a = 8.52₆ Å), all cubic Elpasoliths of pink colour. The Madelung-Part of lattice energy, MAPLE, is calculated and discussed.     

Rubidiumhexaamidolanthanat und -neodymat,Rb3[La(NH2)6] und Rb3[Nd(NH2)6]; Strukturverwandtschaft zu K3[Cr(OH6)] und K4CdCl6

Rubidium Hexaamidolanthanate and -neodymate, Rb₃[La(NH₂)₆] and Rb₃[Nd(NH₂)₆]; Compounds. Structurally Related to K₃[Cr(OH)₆] and K₄CdCl₆ Colourless Rb₃[La(NH₂)₆] (a = 12.298(4) Å, c = 13.759(2) Å, N = 6, R3 c) and pale blue Rb₃[Nd(NH₂)₆] (a = 12.199(6) Å, c = 13.626(4) Å, N = 6, R32) have been prepared by the reaction of the corresponding metals (Rb: La resp. Nd = 3:1) with NH₃(P(NH₃) = 4–4.5 kbar) at 300°C. Single crystal x-ray methods gave their structures. It is shown by space group relations that these compounds are structurally related to one another and to further ternary amides as well as to K₃[Cr(OH)₆] and K₄CdCl₆.