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.     

Das erste Oxomanganat(III) mit Inselstruktur: Zur Kenntnis von Na5[MnO4]

The First Oxomanganate (III) with Isolated Anion Structure. On Na₅[MnO₄] For the first time, Na₅[MnO₄] has been prepared from the binary oxides [500°C, 14 d, Ag-cylinders] as a red powder and in form of red single crystals. The orthorhombic structure (a = 5.822, b = 7.769, c = 6.005 Å, 609 I_o(hkl), R = 0.030, MoKα, 2-circlediffractometer data (Stasi, Fa. Stoe)) is characterized by strongly compressed [MnO₄] groups. Effective coordination numbers, ECoN, as well as the madelung part of lattice energy, MAPLE, are calculated and discussed.     

Na4ReN3, das erste Alkalimetall‐Nitridorhenat(V)

Na₄ReN₃, the First Alkali Metal Nitridorhenate(V) Rhenium powder reacts in a mixture with NaNH₂ in autoclaves at 773 K to orange colored crystals embedded in a matrix of sodium metal. After extracting the sodium metal with liquid ammonia single crystals were seperated. The structure was solved by X‐ray single crystal methods and for the evaluation of the correct space group by optical SHG experiments: spacegroup Cc (No. 9), Z = 4, a = 10.903(2) Å, b = 6.022(1) Å, c = 8.944(2) Å, β = 115.57(3)°. The structure contains trigonal pyramidal anions ReN₃^4–, which are embedded in three‐dimensionally linked, fourfold capped cubes of 12 Na.     

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”?.     

Beiträge zur Chemie des Phosphors. 142. P6(t-Bu)5H – das erste Cyclotetraphosphan mit P2-Seitenkette

Contributions to the Chemistry of Phosphorus. 142. P₆(t-Bu)₅H – the First Cyclotetraphosphane with a P₂ Side Chain The thermolysis of 1, 2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H, leads to formation of the hitherto unknown hexaphosphane P₆(t-Bu)₅H ( 1 ). In the first instance the iso-P₅H₅ derivative P₅(t-Bu)₄H [3] is formed, which reacts further with H₂(t-BuP)₂ or H₂(t-BuP)₃ yielding 1 . Compound 1 has been isolated in the pure state and structurally characterized as 1-(1,2-di-tert-butyldiphosphino)-2, 3, 4-tri-tert-butyl-cyclotetraphosphane, i. e. as a four-membered ring compound with a P₂ side chain. Due to the chirality of the P atoms in the side chain, 1 exists as a mixture of two configurational isomers, the threo-and the erythro-form.     

Beiträge zur Chemie des Phosphors. 138. P5(t-Bu)4H – das erste Derivat von iso-P5H5

Contributions to the Chemistry of Phosphorus. 138. P₅(t-Bu)₄H — the First Derivative of iso-P₅H₅ The thermolysis of 1,2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H, yields under suitable conditions the compound P₅(t-Bu)₄H ( 1 ) as the main product. Besides, the tert-butylphosphanes t-BuPH₂, P₆(t-Bu)₅H ( 2 ), H₂(t-BuP)₃, and (t-BuP)₄ are formed. 1 has been isolated in the pure state and structurally characterized as 1-(tert-butylphosphino)-2,3,4-tri-tert-butyl-cyclotetraphosphane. Hence, compound 1 is a derivative of iso-P₅H₅ with a branched phosphorus skeleton built up by a four-membered ring and a phosphorus side chain.     

Na4SeO5, ein neues Pentaoxoselenat(VI) – Synthese,Charakterisierung und Vergleich mit isotypem Na4MoO5

Na₄SeO₅, a Novel Pentaoxoselenate(VI) – Synthesis, Charakterisation, and Comparison with Na₄MoO₅ Na₄SeO₅ was prepared by high pressure solid state reaction at 500 °C and at a hydrostatic pressure of 2.5 Gpa from a mixture of Na₂O and Na₂SeO₄ in silver crucibles and Na₄MoO₅ by solid state reaction at 450 °C from a mixture of Na₂O and MoO₃. The crystal structures of both new compounds were solved and refined using X‐ray powder methods (Profilematching Na₄SeO₅: P1, a = 988.3(1), b = 988.4(1), c = 558.6(1) pm, α = 96.25(1)°, β = 96.24(1)°, γ = 113.41(1)°, R_p = 0.0783, R_wp = 0.1037. Profilematching Na₄MoO₅: P1, a = 999.5(1), b = 1002.0(1), c = 565.1(1) pm, α = 96.54(1)°, β = 96.29(1)°, γ = 113.35(1)°, R_p = 0.0623, R_wp = 0.0867). Both compounds contain novel XO₅^4– anions of approximately tetragonal pyramidal shape. The crystal structures are consistent with spectroscopic data (IR, Raman).     

Na9[FeO3][FeO4] ein gemischtvalentes Oxoferrat(II,III) mit isolierten [FeO3]4— — und [FeO4]5— ‐Anionen

Na₉[FeO₃][FeO₄]a Mixed Valent Oxoferrat(II, III) with Isolated [FeO₃]^4— — and [FeO₄]^5— Anions Na₉[FeO₃][FeO₄] has been formed and obtained from a redox reaction between CdO and iron metal (reaction container) and Na₂O in the presence of NaOH at 450 °C as orange‐red transparent single crystals. The crystal structure determination (IPDS data: Pca2₁, a = 956.2(2) pm, b = 999.1(2) pm, c = 1032.3(2) pm, Z = 4, R_all = 0.0455) reveals the presence of isolated complex anions, [FeO₃]^4— and [FeO₄]^5—.