NaAuGe,ein weiteres ternäres Aurid mit ethan-analogen Ge2Au6-Baueinheiten

NaAuGe, a Further Ternary Auride with Ethane Analogous Ge₂Au₆ Building Units Black, brittle single crystals of NaAuGe were obtained by the reaction of NaN₃, gold sponge and germanium at 800°C. The structure was determined from X-ray single-crystal diffractometry data: space group Imm2, Z = 4, a = 4.422(1) Å, b = 7.238(2) Å, c = 7.531(2) Å, R1/wR2 = 0.0195/0.0482, N(F) ≥ 2σ(F) = 811 and N(var.) = 21. NaAuGe crystallizes in a new ternary variant of the KHg₂ (CeCu₂)structure type. Gold and germanium form puckered [AuGe_3/3] layers with trigonal planar coordinated gold. The [AuGe_3/3] nets are connected to a framework structure via Ge—Ge contacts along [010] which consist of ethane analogous Ge₂Au₆ building units. The sodium atoms are placed in channels of the Au—Ge framework structure which run along [100] and [010].     

Cs4Au7Sn2: eine Gold–Zinn-Gerüststruktur mit [Au7]-Clustern und Sn2-Hanteln

Cs₄Au₇Sn₂: a Gold Tin Framework Structure with Au₇ Clusters and Sn₂ Dumb-Bells Silver coloured, brittle single crystals of Cs₄Au₇Sn₂ were synthesized by reaction of caesium azide with gold sponge and tin powder at T = 920 K. The structure of the compound (space group R3m, Z = 3, a = 6.844(1) Å, c = 29.233(5) Å) was determined from X-ray single-crystal diffractometry data. Gold and tin form a framework structure that consists of interconnected [Au₇] clusters and Sn₂ dumb-bells. The caesium atoms accupy channel-like cavities within the gold tin partial structure.     

K3Au5Pb: eine Schichtstruktur mit [AuAu3/2]-Gold-Tetraedern und [Pb2/2]-Blei-Ketten

K₃Au₅Pb: Layers of [AuAu_3/2] Gold Tetrahedra and [Pb_2/2] Lead Chains Silver coloured, brittle single crystals of K₃Au₅Pb were synthesized by reaction of potassium azide with gold sponge and lead powder at T = 920 K. The structure of the compound (space group Imma, Z = 4, a = 5.646(1) Å, b = 19.500(4) Å, c = 8.412(1) Å) was determined from X-ray single-crystal diffractometry data. The gold lead partial structure consists of layers of [AuAu_3/2] tetrahedra and [Pb_2/2] zigzag chains with four-bonded lead atoms which are connected to a framework structure via Au–Pb contacts. The potassium atoms occupy channels within the gold lead partial structure.     

K4Au7Ge2: eine Gerüststruktur mit Au7-Doppeltetraedern und Ge2-Hanteln

K₄Au₇Ge₂: a Framework Structure with Au₇-Double-Tetrahedra and Ge₂-Dumb-Bells Black lustrous, brittle single crystals of a hitherto unknown K₄Au₇Ge₂ were synthesized by the reaction of KN₃, germanium- and gold-powder at 550°C. The structure was determined from X-ray single-crystal diffractometry data: space group R3 m, Z = 3, a = 6.411(3) Å, c = 27.912(20) Å, R/R_w(w = 1) = 0.046/0.056, Z(F ${}_{\text{º}}^{\text{2}}$ ) ≥ 3σ(F ${}_{\text{º}}^{\text{2}}$ ) = 302 and N(var.) = 18. K₄Au₇Ge₂ crystallizes in a substitution variant of the MgCu₂-type. Gold and germanium form a framework structure that consists of corner-sharing Au₇-double-tetrahedra and Ge₂-dumb-bells. The potassium atoms occupy channel-like cavities within the gold germanium partial structure.     

Na4AuTl,die erste ternäre Verbindung im System Natrium/Gold/Thallium

Na₄AuTl, the First Ternary Compound in the System Sodium/Gold/Thallium Silver coloured, brittle single crystals of Na₄AuTl were obtained by the reaction of NaN₃, gold sponge and TlN₃ at 773 K. The structure was determined from X-ray single-crystal diffractometry data: Na₄AuTl crystallizes in a new structure type with separated gold and thallium partial structures. These consist of linear [Au_2/2] chains and [Tl₂] dumb-bells. Structural relationships between Na₂Au and the Na Au partial structure of Na₄AuTl are discussed.     

Isolierte [M6S14]-Baueinheiten in ternären Sulfiden des Technetiums und Rheniums

Isolated [M₆S₁₄] Units in Ternary Sulfides of Technetium and Rhenium We have successfully prepared the ternary sulfides Rb₁₀Tc₆S₁₄, Cs₁₀Tc₆S₁₄, Rb₁₀Re₆S₁₄, and Cs₁₀Re₆S₁₄ by heating alkali carbonate with elemental technetium or rhenium in a hydrogen stream charged with sulfur. Structural investigations on single crystals revealed that these compounds crystallize in the space group Fm3 m. [M₆S₁₄] cluster units (M $ \hat = $ Tc, Re) are found as the characteristic structural features, in which regular M₆ octahedra are coordinated by sulfur atoms over their eight faces and six vertices. Other than in the case of the previously investigated ternary technetium and rhenium chalcogenides, these units are not linked to one another, but occur as isolated complex anions which form a cubic close packed array. The alkali ions, whose sites are partly statistically occupied, are found on the corners, the edges and the longer face diagonals of a rhombic dodecahedron surrounding each of these units. The dodecahedra share all their faces with one another. The diamagnetic behaviour which was measured on Cs₁₀Tc₆S₁₄ in the temperature range from 10 to 295 K is in accordance with a 24-electron-configuration of the regular M₆ octahedra.     

Synthese und Struktur von Ba10[Ti4N12], ein ternäres Nitrid mit vierkernigen cyclischen Nitridotitanat-Ionen

Synthesis and Structure of Ba₁₀[Ti₄N₁₂], a Ternary Nitride with Tetranuclear Cyclic Nitridotitanate Ions Ba₁₀[Ti₄N₁₂] results from the reaction of Ba₃N₂, TiN, and N₂ at 980°C. It crystallizes in the triclinic space group P1 with the lattice parameters a = 644.3(4); b = 942.9(7); c = 966.9(7) pm, α = 106.37(4)°; β = 102.22(4)°; γ = 108.56(4)°, Z = 1. The crystal structure is built up by Ba²⁺ cations and tetranuclear cyclic nitridotitanate(IV) anions. In the anions four TiN₄ tetrahedra are each connected by two corners to form centrosymmetrical rings, which are stacked along [100] forming tubes. The Ti? N distances range from 192 to 199 pm.     

Goldreiche Auride mit Caesium: Cs1,34Rb0,66RbAu7 und Cs1,60Rb0,40RbAu7

Gold-rich Aurides with Caesium: Cs_1.34Rb_0.66RbAu₇ and Cs_1.60Rb_0.40RbAu₇ Cs_1,60Rb_0,40RbAu₇, Raumgruppe Cmmm, Z = 2, a = 5,677(1) Å, b = 13,273(3) Å, c = 7,288(1) Å, R1/wR2 = 0,0392/0,0892, Z(F) ≥ 2σ(F) = 700 and Z(Var.) = 23. Silver coloured, brittle single crystals of Cs_1.34Rb_0.66RbAu₇ and Cs_1.60Rb_0.40RbAu₇ were obtained by the reaction of CsN₃, RbN₃ and gold sponge at 903 K. The structures were determined from X-ray single-crystal diffractometry data: Cs_1.34Rb_0.66RbAu₇, space group Cmmm, Z = 2, a = 5.657(1) Å, b = 13.265(4) Å, c = 7.281(2) Å, R1/wR2 = 0.0373/0,0628, N(F) ≥ 2σ(F) = 818 and N(var.) = 23.     

SmAlF5 — ein neues SmII-fluoroaluminat mit Al2F10-Oktaederdoppeln und [AlF2/2F4/1]-Ketten

SmAlF₅ — a New Samarium(II) Fluoroaluminate with Al₂F₁₀ Bioctahedra and [AlF_2/2F_4/1] Chains . SmAlF₅ has been obtained as orange-red transparent single crystals while heating mixtures of SmF₃, Sm-powder and AlF₃ (2:1:3) in a niobium crucible under Ar after 7?10 d at about 750°C. SmAlF₅ crystallises in I 4/m (Nr. 87) with a=1 414.4(4), c=722.2(3) pm and Z=8 (CAD4, 4 340 I_O, R_w=1.7%). The crystal structure of SmAlF₅ is isotypic to BaTiF₅. Characteristic building units are linear chains of trans-corner sharing AlF₆ octahedra, which are connected via corners to two further AlF₆ octahedra. Isolated Al₂F₁₀ octahedra lie disordered between such chains. The Sm atoms connect the AlF₆ octahedra to a three-dimensional network. Measurements of the magnetic susceptibility show the temperature dependence typically found for Sm²⁺. The Madelung part of the lattice energy has been calculated and is discussed.     

Einkristallzüchtung und Strukturverfeinerung von RbAu und CsAu

Single-Crystal Growth and Structure Refinement of RbAu and CsAu Single-crystals of RbAu and CsAu were obtained by the reaction of the alkalimetal azides with gold-powder at 400°C. The structures were determined from X-ray single-crystal diffraktometer data: space group Pm3m, Z = 1; RbAu, a = 4.098(1) Å, R/R_w(w = 1) = 0.011/0.011, N(F_o²) ≥ 3σ(F_o²) = 41 and N(var.) = 4; CsAu, a = 4.258(1) Å, R/R_w(w = 1) = 0.009/0.010, N(F_o²) ≥ 3σ(F_o²) = 34 and N(var.) = 4. Both compounds crystallize in the completely ordered CsCl-type with neglible deviations from the ideal 1:1-composition.     

K2Br(OH) und Rb2Br(OH): Zwei neue ternäre Alkalimetallhalogenidhydroxide mit ausgeprägter Strukturverwandtschaft zu KOH bzw. RbOH

K₂Br(OH) and Rb₂Br(OH): Two New Ternary Alkali Metal Halide Hydroxides with a Pronounced Structural Relationship to KOH resp. RbOH Two isotypic compounds K₂Br(OH) and Rb₂Br(OH) were prepared in the systems KOH/KBr and RbOH/RbBr. Their structures were determined by single crystal X-ray methods: K₂Br(OH): P2₁/m, Z = 2, a = 6.724(1) Å, b = 4.272(4) Å, c = 8.442(2) Å, β = 108.14(2)°, Z(F_o) = 651 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.041/0.047 Rb₂Br(OH): P2₁/m, Z = 2, a = 6.918(3) Å, b = 4.483(2) Å, c = 8.850(5) Å, β = 108.08(6)°, Z(F_o) = 326 mit (F_o)² ≥ 3σ(F_o)², Z(parameter) = 27, R/R_w = 0.074/0.082. The compounds are built up by chains of [M₂(OH)⁺] connected via Br^?. The structure of the chains as well as their orientation to one another show a pronounced relationship to the structures of the room temperature modifications of the isotypic binary hydroxides KOH and RbOH.     

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).     

NaAg3S2, ein Thioargentat mit dem Clusteranion [Ag6S4]2−

NaAg₃S₂, a Thioargentate Containing the Anionic Cluster [Ag₆S₄]^2? . Dark-red octahedrally shaped crystals of NaAg₃S₂ could be obtained by the reaction of NaAg(CN)₂ and NaCN in a stream of hydrogen sulfide at 630 K. NaAg₃S₂ crystallizes cubic, a=12.358(1) Å, space group Fd3 m, Z=16. The structure was determined from four-circle diffractometer data. NaAg₃S₂ contains the anionic cluster [Ag₆S₄]^2?. The structure can be traced back to the spinel structure typ. An extended Hückel calculation for the cluster anion, which is considered to be isolated, shows weak bonding silver-silver interactions. NaAg₃S₂ is diamagnetic at room temperature.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Zintl-Verbindungen mit Gold: M3AuSn4 mit M = K,Rb, Cs und M3AuPb4 mit M = Rb,Cs

Zintl-Compounds with Gold: M₃AuSn₄ with M = K, Rb, Cs and M₃AuPb₄ with M = Rb, Cs Silver coloured, brittle single crystals of the compounds M₃AuSn₄ with M = K, Rb, Cs and M₃AuPb₄ with M = Rb, Cs were synthesized by reactions of alkali metal azides (MN₃) with gold sponge and tin (lead) powder at T = 923 K. The structures of the isotypic compounds (space group Pmmn, Z = 2) were determined from X-ray single-crystal diffractometry data (see ‘‘Inhaltsübersicht”︁”︁). The Zintl-compounds M₃AuE(14)₄ with E(14) = Sn, Pb contain [AuE(14)₄]-chains with P₄-analogous E(14)₄-tetrahedra which are connected by μ₂-bridging gold atoms.     

Na5Br(OH)4: Darstellung und Kristallstruktur einer Verbindung im System NaOH/NaBr

Na₅Br(OH)₄: Synthesis and Structure of a Compound in the System NaOH/NaBr The pseudobinary system NaOH/NaBr is investigated by X-ray methods. The structure of the compound Na₅Br(OH)₄ was solved by single crystal data: Na₅Br(OH)₄: Pnma, Z = 8, a = 11.846(2) Å, b = 18.782(4) Å, c = 6.431(1) Å, Z(F_o) = 1 202 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 100, R/R_w = 0.030/0.035 The compound crystallizes in a new type of structure. Pairs of octahedra around O by 5 Na and 1 H to [Na₅(OH)]₂ are orientated in such a way to one another that two ions OH^? form a parallelogram hinting to unusual bent hydrogen bridge bonding.     

PrSeTe2, ein geordnetes ternäres Polychalkogenid mit NdTe3‐Struktur

PrSeTe₂, an Ordered Ternary Polychalcogenid with NdTe₃ Structure Single crystals of PrSeTe₂ have been obtained by reaction of the elements in a LiCl/RbCl flux at 970 K during 7 days. PrSeTe₂ crystallizes in space group Cmcm (No. 63), with four formula units per unit cell. The lattice constants are a = 426.1(1) pm, b = 2506.0(5) pm, and c = 426.0(1) pm. The crystal structure is an ordered ternary variant of the NdTe₃ type. It consists of a puckered double layer of praseodymium and selenium atoms [PrSe] sand wiched by two square planar layers of tellurium atoms [Te] yielding a stacking —[Te]—[Te]—[PrSe]— along [010]. The Te atoms build regular 4⁴ nets with Te—Te distances of 301, 3(1) pm. DFT calculations propose that this compounds should be metallic mainly due to contributions of the Pr f‐electrons. The band structure shows no significance for a distortion in the [Te]—nets.     

Na8Au11In6: ein Gold – Indium-Polyedergerüst mit pentagonal-bipyramidalen AuAu5In-Baueinheiten

Na₈Au₁₁In₆: a Gold Indium Polyhedra Framework with Pentagonal Bipyramidal AuAu₅In Building Units Silver coloured, brittle single crystals of a hitherto unknown Na₈Au₁₁In₆ were synthesized by the reaction of NaN₃, indium and gold sponge at 500°C. The structure was determined from X-ray single-crystal diffractometry data: space group Pbcm, Z = 4, a = 5.483(1) Å, b = 25.663(2) Å, c = 15.046(5) Å, R1/wR2 = 0.036/0.087, Z(F) = 3σ(F) = 2584 and N(var.) = 125. Na₈Au₁₁In₆ crystallizes in a new structure type. The gold indium partial structure contains tetrahedral [Au₂AuIn]^T and pentagonal bipyramidal [AuAu₅In]^PBP building units which are connected to a three-dimensional framework via Au In exo-bonds and bridging gold and indium atoms. The interconnection pattern of the polyhedra is described by the formula [Au₂AuIn]^TIn_4/2^i-iAu₂^aIn₂^a [AuAu₅In]^PBP according to the notation for transition metal clusters. The sodium atoms are placed in channel like cavities within the gold indium partial structure, which run along [100]. Structural relationships between Na₈Au₁₁In₆ and Friauf Laves phases are discussed.     

Zur Kenntnis von Na4Br(NH2)3: Ein Amidbromid im System NaNH2/NaBr

Na₄Br(NH₂)₃: An Amide Bromide in the System NaNH₂/NaBr The pseudobinary system NaNH₂/NaBr was investigated by X-ray methods. The crystal structure of Na₄Br(NH₂)₃ was solved by single crystal data: Pnnm, Z = 4, a = 6.579(2) Å, b = 12.755(4) Å, c = 8.776(2) Å Z(F_o) with (F_o)² ≥ 3σ = (F_o)² = 503, Z(parameter) = 39, R/R_w = 0.082/0.106. It is a new type of structure, built up by a three-dimensional network of [Na₄(NH₂)₃⁺] containing the bromide ions.     

Verbindungen in den Systemen Kalium(Rubidium)/Gold/Antimon: K3Au3Sb2, Rb3Au3Sb2 und K1,74Rb0,26RbAu3Sb2

Compounds in the Systems Potassium(Rubidium)/Gold/Antimony: K₃Au₃Sb₂, Rb₃Au₃Sb₂, and K_1,74Rb_0,26RbAu₃Sb₂ Brittle, silver coloured single crystals of K₃Au₃Sb₂, Rb₃Au₃Sb₂ and K_1,74Rb_0,26RbAu₃Sb₂ were obtainded by reaction of the alkali metal azides (KN₃, RbN₃) with gold and antimon powder at 550°C. The structures of the isotypic compounds (R3 m, Z = 3) were determined by X-ray single-crystal diffractometer data: K₃Au₃Sb₂, a = 6,198(2) Å, c = 21,520(5) Å, R/R_w (w = 1) = 0,046/0,058, Z(F) ? 3σ(F) = 175, Z(Var.) = 14; Rb₃Au₃Sb₂, a = 6,443(3), c = 21,69(2), R/R_w (w = 1) = 0,059/0,082, Z(F) ? 3σ(F₀²) = 258, Z(Var.) = 14; K_1,74Rb_0,26RbAu₃Sb₂, a = 6,288(2) Å, c = 21,617(5) Å, R/R_w (w = 1) = 0,049/0,069, Z(F) ? 3σ(F) = 390, Z(Var) = 14. The compounds crystallize with the K₃Cu₃P₂-structure type. The Au? Sb partial structures consist of [AuSb_2/3] layers with linear Sb? Au? Sb dumb-bells and SbAu₃ pyramids. The layers are separated by two crystallographically independent alkali metal atoms along [001].