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].     

Force field,vibrational modes,and conformations for (t-BuO)3Sb AND (i-PrO)3Sb

By solving the inverse spectral problem for the (t-BuO)₃Sb molecule, we have obtained force constants for the Sb(OC)₃ fragments having the property of transferability. Rotation about the SbO bond weakly affects the frequencies of the skeletal vibrations of (RO)₃Sb molecules (R=t-Bu, i-Pr), while rotations of the propyl radicals about the OC bond lead to significant changes in the frequencies. In an equilibrium mixture of conformers of (i-PrO)₃Sb molecules, forms must be present with gauche orientation of the methine protons relative to the SbO bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2547–2551, November, 1989.     

121Sb Mössbauer spectra of alkali metal antimonides M3Sb (M3 = Na3, K3, Na2K, Rb3)

¹²¹Sb Mössbauer spectra for M₃Sb (M₃ = Na₃, K₃, Na₂K, Rb₃) were measured at 12 K. The values of isomer shift (d) and quadrupole coupling constant suggest that the valence state of antimony in M₃Sb is –3. The d values increase in the order Rb₃Sb<K₃Sb<Na₃Sb<Na₂KSb. The differences in d values are discussed by examining M–Sb distances and bond valence for M–Sb interactions. Some covalent interactions between alkali metal atoms and antimony atom are suggested.     

Barium antimonide oxide,Ba3Sb2O

The antimonide oxide Ba₃Sb₂O consists of discrete [Sb₂]^4? and O^2? anions, and crystallizes with a new structure type. The Sb—Sb distances are comparable to those known from electron‐precise zintl phases and the tetrahedral coordination of the O^2? anion is also observed in some other Ba‐rich metallide oxides.     

Das Zintl-Konzept als Syntheseprinzip: Darstellung und Kristallstrukturen von K2Ba3Sb4 und KBa4Sb3O

Starting from the Zintl-Concept: Syntheses and Crystal Structures of K₂Ba₃Sb₄ and KBa₄Sb₃O The black, metallic lustrous, air sensitive compounds K₂Ba₃Sb₄ and KBa₄Sb₃O were prepared from melts of mixtures of the elements, in case of KBa₄Sb₃O with a stoichiometric amount of Sb₂O₃. K₂Ba₃Sb₄ crystallizes in the orthorhombic system, space group Pnma (a = 870.5(1) pm, b = 1770.2(2) pm, c = 923.6(1) pm, Z = 4) and is the first Sb compound with only [Sb₂]^4– dumbbells in the anionic partial structure. The compound KBa₄Sb₃O crystallizes in the tetragonal system, space group I4/mcm (a = 882.4(1) pm, c = 1659.4(2) pm, Z = 4). In this structure antimony forms [Sb₂]^4–-dumbbells and isolated ions Sb^3–. Each antimony ion of the dumbbells – in K₂Ba₃Sb₄ as well as in KBa₄Sb₃O – is coordinated in form of a bicapped skew trigonal prism. The isolated Sb^3– ions in KBa₄Sb₃O center bicapped tetragonal antiprisms, the O^2– ions occupy tetrahedral voids.     

Neutrale Thiolate und ein Iodidthiolat von Antimon(III). Die Kristallstrukturen von Sb(SC6H5)3, Sb(SC6H2Me3-2,4,6)3 und SbI(SC6H2Me3-2,4,6)2

Neutral Thiolates and a Iodothiolate of Antimony(III). Crystal Structures of Sb(SC₆H₅)₃, Sb(SC₆H₂Me₃-2,4,6)₃, and SbI(SC₆H₂Me₃-2,4,6)₂ The crystal structures of Sb(SC₆H₅)₃ ( 1 ), Sb(SC₆ · H₂Me₃-2,4,6)₃ ( 2 ), and the novel compound SbI(SC₆H₂Me₃-2,4,6)₂ ( 3 ) have been determined by X-ray crystallography. In addition to the expected trigonal pyramidal coordination of antimony intermolecular interactions are observed for 1 (Sb … O: 363.3 pm) and 3 (Sb … S: 2 × 369.4 pm) but not for 2 . The reasons for these differences are discussed.     

Synthese und Strukturanalyse von Na3SbSe3·3Sb2O3·0,5Sb(OH)3

Investigations in the system Sb-Se-NaOH-H₂O, hydrothermal conditions, yielded crystals of the compound Na₃SbSe₃·3Sb₂O₃·0,5Sb(OH)₃. The structure of this compound (a=14.40 Å,c=5.568 Å; space group P 6₃-C ₆ ⁶ ;Z=2) was determined from 985 independent X-ray intensities — collected on an automaticWeissenberg type diffractometer — by thePatterson method and refined by the least squares method toR=8.3% (with -weighting 5.9%). The structure consists of SbO₃ pyramids which are connected via common oxygen corners to tubes parallel [001]. These tubes and SbSe₃ pyramids are combined by Na atoms to a framework. The Sb(OH)₃ groups are statistically located within the channels of the tubes.

     

First principles prediction of the elastic,electronic, and optical properties of Sb2S3 and Sb2Se3 compounds

We have performed a first principles study of structural, mechanical, electronic, and optical properties of orthorhombic Sb₂S₃ and Sb₂Se₃ compounds using the density functional theory within the local density approximation. The lattice parameters, bulk modulus, and its pressure derivatives of these compounds have been obtained. The second-order elastic constants have been calculated, and the other related quantities such as the Young's modulus, shear modulus, Poisson's ratio, anisotropy factor, sound velocities, Debye temperature, and hardness have also been estimated in the present work. The linear photon-energy dependent dielectric functions and some optical properties such as the energy-loss function, the effective number of valence electrons and the effective optical dielectric constant are calculated. Our structural estimation and some other results are in agreement with the available experimental and theoretical data.     

Darstellung und Kristallstruktur von ANi10P3 (A: Zn,Ga, Sn,Sb)

Preparation and Crystal Structure of A Ni₁₀P₃ ( A : Zn, Ga, Sn, Sb) Four compounds ANi₁₀P₃ (A: Zn, Ga, Sn, Sb) were prepared by heating mixtures of the elements and investigated by means of X‐ray methods. Single crystal structure determinations of ZnNi₁₀P₃ (a = 7.665(1), c = 9.360(1) Å) and SnNi₁₀P₃ (a = 7.674(1), c = 9.621(1) Å) respectively showed, that they are isotypic and crystallize in a new structure (P3m1; Z = 3). This type is characterized by 3²⁰ and 3²⁴ cages of Ni atoms (Frank Kasper polyhedra), which are connected with each other. A atoms are located in the centres of these polyhedra and have no direct bonds to the P atoms.     

Expanding the 0D Rb7M3X16 (M=Sb,Bi; X=Br,I) Family: Dual-Band Luminescence in Rb7Sb3Br16

Inorganic, lead-free metal halides are widely sought after following the rise of the halide perovskites as outstanding optoelectronic materials, due to their enhanced stability and reduced toxicity. Herein, we report on the solvothermal synthesis of Rb₇Sb₃Br₁₆, which exhibits a 0D structure comprised of [SbBr₆]³⁻ octahedra and edge-sharing bioctahedra [Sb₂Br₁₀]⁴⁻ dimers that order into layers along the c-axis. This all-inorganic material is air-stable and exhibits weak orange photoluminescence (PL) at room temperature. Low-temperature PL and PL excitation (PLE) measurements reveal the presence of two distinct emission bands that originate from these structural units, with the high-energy emission quenching as temperature rises beyond 150 K. We are also able to obtain Rb₇Bi₃Br₁₆ and Rb₇Bi₃I₁₆ which both crystallize in orthorhombic symmetry, with Rb₇Bi₃Br₁₆ presenting weak low-temperature luminescence while Rb₇Bi₃I₁₆ is non-luminescent. This work expands the library of emissive inorganic metal halides and provides further evidence for the efficacy of low-dimensional Sb−X luminescent centers based on octahedral and edge-sharing [Sb₂X₁₀]⁴⁻ dimers.     

Novel Antimony Complexes: [Ph4Sb]4 +[Sb4I16]4− · 2Me2C=O and [Ph4Sb]3 +[Sb5I18]3−

The [Ph₄Sb]₄ ⁺[Sb₄I₁₆]^4– · 2Me₂C=O and [Ph₄Sb]₃ ⁺[Sb₅I₁₈]^3– complexes were synthesized by reacting tetraphenylstibonium salts Ph₄SbX (X = I, OSO₂C₆H₄Me-4) with antimony triiodide in acetone. According to X-ray diffraction data, their tetra- and pentanuclear anions [Sb₄I₁₆]^4– and [Sb₅I₁₈]^3– have cyclic and linear structure, respectively.     

Darstellung,spektroskopische und röntgenographische Untersuchung von monomerem Sb(CCCH3)5 und dimerem Sb(OCH3)5

Preparation, Spectroscopic and X-Ray Structure Investigations of Monomeric Sb (CCCH₃)₅ and Dimeric Sb (OCH₃)₅ Prop₃SbCl₂ (Prop ? C?C? CH₃) reacts with NaProp to form SbProp₅. This compound is monomeric in solution and in solid state and has according to the vibrational spectra a trigonal-bipyramidal structure of D_3h symmetry. The X-Ray structure determination shows the monoclinic space group C2/c with 8 formula units per cell. Dimeric Sb(OMe)₅ (Me ? CH₃) is formed by the interaction of SbProp₅ with MeOH in an 1:5 molar ratio. The structure is determined by ¹H, ¹³C-NMR, IR and Raman spectra and the crystal structure of this alkoxide is described.     

Observation of Sb2O3 Nanocrystals in SiO2 after Sb Ion Implantation

 Antimony nanocrystals were formed in thin SiO₂ films using low-energy ion implantation of Sb followed by annealing. Using Fourier transform laser microprobe mass spectrometry (FT LMMS), we observed for the first time the presence of antimony oxide in the intermediate phase (as-implanted layer of Sb) by means of signals referring to the intact Sb₂O₃ molecules. Only SbO⁺ fragments, but no adduct ions of Sb₂O₃ could be detected in annealed samples. The size and the distribution of the nanocrystals formed around the initial depth of implantation were studied in the as-implanted samples by high-resolution electron microscopy (HREM). The crystalline structure of these nanocrystals was also studied and the presence of antimony trioxide Sb₂O₃ in the form of valentinite was proven. After the annealing step, the implanted material had spread into a wider band. The method introduced here, based on combining TEM (transmission electron microscopy) and FT LMMS results, offers the possibility of studying the evolution of the phases in Sb nanocrystal formation.     

Schwingungsspektren und Kraftkonstanten von W(OCH3)6, Mo(OCH3)6 und [Sb(CH3)4][Sb(OCH3)6]

Vibrational Spectra and Force Constants of W(OCH₃)₆, Mo(OCH₃)₆, and [Sb(CH₃)₄][Sb(OCH₃)₆] The infrared and Raman spectra of the monomeric hexamethoxides of Tungsten and Molybdenum and of the ionic compound [Me₄Sb]⁺[Sb(OMe)₆]^? (prepared from [Sb(OMe)₅]₂ and Me₄SbOMe; Me = CH₃) are recorded and interpreted on the basis of C_3i symmetry. The force fields of W(OMe)₆ and [Sb(OMe)₆]^? are calculated using the same basis set of force constants. Both W? O- and Sb? O- stretching force constants are identical (2.56 N/cm), however the other parts of the valence force field are markedly different.     

K3SbS3 · 3Sb2O3, ein Oxothioantimonit mit Röhrenstruktur

K₃SbS₃ · 3 Sb₂O₃, an Oxothioantimonite with a Tube Structure Orange colored K₃SbS₃ · 3 Sb₂O₃ was prepared in an alkaline aqueous solution of K₂S and Sb₂S₃. It crystallizes in thin hexagonal prisms. For crystallographic data see ?Inhaltsübersicht”?. There are Sb₂O₃-tubes in this structure. Inside these tubes are the K⁺-ions. Their charge is neutralized by SbS-pyramides, which occupy positions between the Sb₂O₃ tubes.     

Die Antimonid–Triantimonidometallate(III) Cs6K3Sb[AlSb3] und Cs6K3Sb[GaSb3]

The Antimonide Triantimonidometallates(III) Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] The novel compounds Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] are formed from stoichiometric mixtures of Cs, AlSb (GaSb) and KSb in sealed niobium ampoules at 950 K. The hexagonal structures are especially characterized by one-dimensional rod packings ¹∞[Cs₆K₃Sb] which are formed from columns of condensed (Cs₆K_6/2) icosahedra. The icosahedra are centered by Sb^3-? anions. The trigonal planar anions [AlSb₃]^6-? and [GaSb₃]^6-? are embedded between the icosahedra columns, and they are coordinated by alkali metal atoms. The FIR spectra were assigned to the vibrations of the [MSb₃]^6-? anions, with respect to the 6 m2-D_3h symmetry. (P6₃/mmc, No. 194; a = 1101.7 and 1097.2 pm; c = 1158.9 and 1150.1 pm; Z = 2; Single crystal data: 574 and 546 reflections; R = 0.073 and 0.029. Distances:d(Al? Sb) = 265.4 pm; d(Ga? Sb) = 265.1 pm; d(Sb? Cs) = 401.6–423.0 pm; d(Sb? K) = 358.6–367.3 pm).     

Synthesis,Crystal and Electronic Structure,and Optical Property of the Quaternary Selenide: La3Sb0.33SiSe7

The quaternary selenide, La₃Sb_0.33SiSe₇, was prepared from stoichiometric mixtures of elements by solid‐state reactions at 1223 K in an evacuated silica tube. La₃Sb_0.33SiSe₇ crystallizes in the chiral P6₃ space group and belongs to the Ce₃Al_1.67S₇ structure type. Its structure features one‐dimensional chains of face‐sharing SbSe₆ octahedra running parallel to the c direction surrounded by the discrete SiSe₄ tetrahedra and La cations. UV/Vis/NIR diffuse reflectance spectroscopy study shows its optical gap of around 1.75 eV. DFT study indicates an indirect bandgap with an electronic transfer excitation from Se 4p to La 5d orbital electrons.     

Mischkristallbildung von As2O3 und Sb2O3

Zusammenfassung Durch Wegkochen von NH₃ aus ammoniakalischen Tartratlösungen des As₂O₃ und Sb₂O₃ in verschiedenem Verhältnis wurden einerseits monokline Mischkristalle der Oxyde mit einem Gehalt zwischen 100 und 70 Molprozent Arsen, andererseits kubische Mischkristalle mit 30 bis 100 Molprozent Antimon gewonnen. Die analytischen Ergebnisse werden durch Röntgen- und Infrarot-Untersuchungen bestätigt, aus den letzteren ergeben sich weitere Hinweise auf die Struktur.Mit 1 Abbildung1. Mitt.:E. Hayek, M. Hohenlohe-Profanter, B. Marcic undE. Beetz, Angew. Chem.70 307 (1958).     

From a 1D Sb Coordination Polymer to a 3D Sb Framework with Pyrazine: Switching off the Stereochemically Active Lone-Pair

The one-dimensional coordination polymer ¹_∞[SbCl₃(pyz)] ( 1 ) and the three-dimensional frameworks ³_∞[Sb₂Cl₆(pyz)₃] ( 2 ) and ³_∞[Sb₂I₆(pyz)₃] ( 3 ) were obtained from SbX₃ (X: Cl, I) and pyrazine (pyz). These coordination polymers are, to the best of our knowledge, among the first Sb-based coordination polymers constructed from antimony halides and N-donor ligands. While the Sb³⁺-cations in 1 are coordinated in a square-pyramidal coordination sphere indicating a stereochemically active lone-pair, no stereochemically active Sb-lone-pair is present in 2 and 3 having octahedral coordination spheres around Sb^III. Since 2 can be obtained by heating of 1 , the character of the Sb-lone-pair in 1 can be changed by thermal treatment. Thereby the interlinkage is increased via an additional pyrazine molecule resulting in the octahedral coordination in 2 .     

Sb121 and Sb123 NQR spectra in the compounds R3SbHal2

Conclusions The NQR data on the central antimony atom in R₃SbHal₂ compounds indicate that an interaction between the -system of the equatorial substituents and the vacant d-orbitals of the metal exists.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 484–485, February, 1970.