Zur Neuuntersuchung des Phasendiagramms TlI—SnI2

Redetermination of the Phase Diagram TlI—SnI² A reinvestigation of the phase diagram TlI—SnI₂ revealed the existence of a not yet known ternary 4 : 1 compound of the formula Tl₄SnI₆, which decomposes peritectoidally at 229^°C. The congruent melting points of the other three ternary compounds in the system, Tl₃SnI₅, TlSnI₃, and TlSn₂I₅, at 329^°C, 292^°C and 307^°C, respectively, agreed well with former specifications. However the polymorphic transitions of the compounds Tl₃SnI⁵ and TlSn₂I₅ described by other authors could not be verified.     

Notiz zur Kenntnis der roten Monohalogenide des Indiums,InX (X = CI,Br, I)

Inhaltsübersicht. Synthese (aus den Elementen; Einkristalle durch Sublimation im Gradienten: 200 → 100°C) und Strukturverfeinerung von InI (orthorhombisch, Cmcm, Z = 4; a = 476,3(1); b = 1278,1(1); c = 490,9(1) pm) werden beschrieben. Ein Vergleich mit InBr und InCl (alle TlI-Typ) weist auf die Bedeutung des 5s²-Elektronenpaares von In⁺ für diesen Strukturtyp und auf attraktive Wechselwirkungen in Richtung auf die Ausbildung eines Dimeren, In₂²⁺, hin. Note on the Red Monohalides of Indium, InX (X = CI, Br, I) Synthesis (from the elements; single crystals by sublimation in a 200 → 100°C gradient) and structure refinement of InI (orthorhombic, Cmcm, Z = 4, a = 476.3(1), b = 1278.1(1), c = 490.9(1) pm) are reported. A comparison with the isotypic halides InBr and InCl (all TlI type) hints at the importance of the 5s² electron pair of In⁺ for this structure type. Attractive interactions in the direction of the formation of a dimer, In₂²⁺, could play a role.     

Zur Kenntnis des quasi-binären Systems InBr—SnBr2

On the Quasi-binary System InBr—SnBr₂ The phase diagram of the quasi-binary system InBr—SnBr₂ is derived from DTA and X-ray investigations. A 1:2, 1:1 and a 3:1 compound are found. InSn₂Br₅ crystallizes tetragonal with the NH₄Pb₂Br₅-type structure. InSnBr₃ shows a new structure type. This compound is stable in a very narrow temperature range only. In₃SnBr₅ can be attributed to the low-temperature-Tl₃PbBr₅-type structure.     

Untersuchungen von nach verschiedenen Verfahren hergestellten Zinnjodiden mit Hilfe des Mössbauer-Effektes

The MÖSSBAUER spectra of various samples of differently prepared Sn^II and Sn^IV iodides have been investigated. — An SnI₂ sample, prepared by dissolving elemental tin in hydroiodic acid, was shown to be strongly contamined with SnI₄; by recrystallisation from ethanol no purification was achieved. However, SnI₂ samples being free from SnI₄ were obtained by precipitation from SnCl₂ solutions by means of HI, KI or NaI. The isomeric shift value of SnI₂ is 3.8 mm/sec. — SnI₄ may be easily prepared from metallic tin and elemental iodine in CHCl₃ or py precipitation from an SnCl₄ solution by means of HI or KI.     

Ternäre Thallium-Indium-Sulfide: Eine Zusammenfassung

Ternary Thallium Indium Sulfides: A Summary Combined thermal and X-Ray analyses in the ternary system Thallium—Indium—Sulfur show, that the two binary sections Tl₂S? In₂S₃ and TlS? InS contain ternary compounds with unique crystal structures. The chemical formulas of these ternary solids are TlIn₅S₈, TlIn₃S₅, TlInS₂ and Tl₃InS₃ for the section Tl₂S? In₂S₃ and TlIn₅S₆ as well as Tl₃In₅S₈ (metastable high temperature phase) for the section TlS? InS respectively. With TlIn₅S₇ an additional ternary solid could be detected, which is located outside the two sections. It is derived from the binary mixed valence compound In₆S₇ by complete substitution of In⁺ by Tl⁺. The following ionic formulations make the mixed valence character of the ternary Thallium—Indium-Sulfides reasonable: TlIn₅S₈ = Tl⁺(In³⁺)₅(S^2?)₈, TlIn₃S₅ = Tl⁺ (In³⁺)₃(S^2?)₅, TlInS₂ = Tl⁺In³⁺(S^2?)₂, Tl₃InS₃ = (Tl⁺)₃In³⁺ · (S^2?)₃, TlIn₅S₆ = Tl⁺([In₂]⁴⁺)₂In³⁺ (S^2?)₆, Tl₃In₅S₈ = 4 × [(Tl⁺)_0,75 · (In⁺)_0,25In³⁺(S^2?)₂], TlIn₅S₇ = Tl⁺[In₂]⁴⁺ (In³⁺)₃(S^2?)₇. All compounds contain Tl⁺-ions in a characteristic “lone pair coordination” of S^2? ions. Indium atoms however occur with the oxidation numbers +2 (formal, In₂ dumb bells with covalent In? In bonding) and +3 (with In³⁺ in tetrahedral and octahedral coordination of S^2?). Chemical preparation, crystal chemistry and general properties of the ternary solids are discussed, summarized and compared to each other.     

Phase study of the system Li2Se-In2Se3

The binary system Li₂Se-In₂Se₃ was investigated in the range of 40 to 100 mol% In₂Se₃ by thermoanalytical and X-ray methods. The system is characterized by two eutectic points. Beside the two binary components and the known ternary compound LiInSe2 another ternary compound crystallizes in this binary system at 83.3 mol% In₂Se₃. This compound was identified as LiIn₅Se₈. In contrast to (Cu, Ag)^IB₅ ^IIIC₈ ^VI compounds such as CuIn₅S₈ [1] it does not crystallize in the spinel structure. LiIn₅Se₈ shows a stratified structure. The melting point was determined to be at 810°C. Starting from room temperature up to the melting point no phase transitions were observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

[SnI8{Fe(CO)4}4]2+: Highly Coordinated Sn+III8 Subunit with Fragile Carbonyl Clips

[SnI₈{Fe(CO)₄}₄][Al₂Cl₇]₂ contains the [SnI₈{Fe(CO)₄}₄]²⁺ cation with an unprecedented highly coordinated, bicapped SnI₈ prism. Given the eightfold coordination with the most voluminous stable halide, it is all the more surprising that this SnI₈ arrangement is surrounded only by fragile Fe(CO)₄ groups in a clip‐like fashion. Inspite of a predominantly ionic bonding situation in [SnI₈{Fe(CO)₄}₄]²⁺, the I^????I^? distances are considerably shortened (down to 371 pm) and significantly less than the van der Waals distance (420 pm). The title compound is characterized by single‐crystal structure analysis, spectroscopic methods (EDXS, FTIR, Raman, UV/Vis, Mössbauer), thermogravimetry, and density functional theory methods.     

SnI4⋅(S8)2: A Novel Adduct‐Type Infrared Second‐Order Nonlinear Optical Crystal

A simple adduct from tin tetraiodide SnI₄ and octasulfur S₈, SnI₄?(S₈)₂ ( 1 ), is obtained employing a facile reaction. The combination of Sn⁴⁺ ions with d¹⁰ electron configuration, acentric SnI₄ tetrahedra, and lone‐pair effects of S₈, makes 1 a phase‐matchable infrared NLO crystal with a moderate second‐harmonic generation (SHG) response and a very high laser‐induced damage threshold (LIDT), which is well confirmed by the DFT calculations.     

Zur Kenntnis des quaternären Systems Zn?In?S?Se Der Schnitt ZnIn2S4?Znln2Se4?In2S3?In2Se3

The Quaternary System ZnIn₂S₄? ZnIn₂Se₄? In₂Se₃? In₂S₃ The title system has been investigated on the indium rich side (ratio In/Zn ≥ 2) on samples quenched from 800°C to room temperature using x-ray methods. In this section 7 different phases could be identified the phase borders of which are given. ZnIn₂S₄-type and thiogallate type mixed crystals only show a small region of homogeneity while the monophase region of spinel type mixed crystals in the indiumsulfide rich part of the phase diagram has a larger extension. There is a new trigonal compound ZnIn₂S₂Se₂ (a_hex = 3.937, c_hex = 31.97 Å) with a large region of homogeneity. In the indiumselenide rich part there are two new phases: (i) Zn_0.4In₂Se_3.4 with unknown structure and (ii) a ternary phase of unknown structure in the system In₂S_3?xSe_x for 2.1 ≤ x ≤ 2.7.     

Diiodobis(4‐methylpentan‐2‐onato‐C4,O)tin(IV): a comparison with diiodobis(3‐methoxy‐3‐oxopropyl‐C,O)tin(IV)

The title compound, [SnI₂(C₆H₁₁O)₂], contains a six‐coordinate tin centre as a consequence of intramolecular Sn—O interactions. The Sn—O bond lengths range between 2.428 (4) and 2.439 (4) Å.     

Indiumwolframat,In2(WO4)3 – ein In3+ leitender Festkörperelektrolyt

Indium Tungstate, In₂(WO₄)₃ – an In³⁺ Conducting Solid Electrolyte Polycrystalline In₂(WO₄)₃ has been electrochemically characterized and unambiguously identified as an In³⁺ conducting solid electrolyte. By heating, indium tungstate undergoes a phase transition between 250 °C and 260 °C transforming from a monoclinic to an orthorhombic phase for which the conduction properties have been determined. The adopted crystal structure in this high temperature region corresponds to the Sc₂(WO₄)₃ type structure. The electrical conductivity was investigated by impedance spectroscopy in the temperature range 300–700 °C and amounts to about 3.7 · 10^–5 Scm^–1 at 600 °C with a corresponding activation energy of 59.5 kJ/mol. Polarization measurements indicated an exclusive current transport by ionic charge carriers with a transference number of about 0.99. In dc electrolysis experiments, the trivalent In³⁺ cations were undoubtedly identified as mobile species. A current transport by oxide anions was not observed.     

REACTIVITY OF HALIDE COMPLEXES OF TIN(II) I. The Reduction of Methyl Orange

Abstract

Halide ion is required for the reduction of methyl orange by Sn(II). Equilibrium data on the formation of SnCl^2-n _n and SnI^2-n _n combined with kinetic data indicate that SnCl₃ ^? and SnI₃ ^? form activated complexes with protonated methyl orange. The data also suggest pathways involving SnCl₄ ^? SnCl₅ ³, SnI₅ ³ and SnI₇ ^5-.     

Synthesis and Structure of Ba8Cu3In4N5 with Nitridocuprate Groups and One-Dimensional Infinite Indium Clusters

Single crystals of the quaternary compound Ba₈Cu₃In₄N₅ were prepared by heating Ba, Cu, and In in a Na flux at 1023 K under 7 MPa of N₂, and by slow cooling from this temperature. The crystal structure was analyzed by single-crystal X-ray diffraction. It crystallizes in an orthorhombic cell (space group Immm (No. 71), Z=2) with a=4.0781(6), b=12.588(2), and c=19.804(3) Å at 298 K. The structural formula is expressed as Ba₈[CuN₂]₂ [CuN]In₄. Nitridocuprates of one-dimensional chains ¹_∞[CuN_2/2] and isolated units ⁰[CuN₂], and one-dimensional indium clusters ¹_∞[In₂In_4/2] are contained in the structure. A split-site model applied for the arrangement of ¹_∞[CuN_2/2] chains suggested that there is a short-bond, long-bond alternation of the Cu-N bondings. The electrical resistivity of Ba₈Cu₃In₄N₅ was 3.44 mΩ·cm at 298 K. A metallic temperature dependence of the resistivity was observed down to 10 K.     

Zur Existenz tetraedrischer Polykationen [In5]7+ in der Verbindung „Na23In5O15”︁ (=Na24In5O15?) einem ungewöhnlichen Oxidationsprodukt der intermetallischen Phase NaIn

Tetrahedral Polycations [In₅]⁷⁺ in ‘‘Na₂₃In₅O₁₅”︁”︁ (=Na₂₄In₅O₁₅?) an Unusual Oxidation Product of the Alloy NaIn The already published, red-transparent, air sensitive, cubic compound Na₂₄In₅O₁₅ (a = 1107.7 pm, Z = 2, I43m) is an intermediate oxidation product of the intermetallic phase NaIn. It is reinvestigated with respect to the question whether it contains the tetrahedral polycation [InIn₄]⁶⁺ or [InIn₄]⁷⁺. In the latter case the chemical composition would be Na₂₃In₅O₁₅ instead of Na₂₄In₅O₁₅ and the polycation would be in accordance with the Zintl-Klemm concept. Na₂₄In₅O₁₅ is prepared in single phased samples for the first time and investigated by means of the Rietveld refinement technique of X-ray powder data. Based on the results of the Rietveld refinements and new single crystal data in comparison to the published values we note anomalies in the occupancies of the Na positions and a pronounced anisotropy in the thermal parameters of one oxygen position. These investigations together with results obtained by analytical scanning electron microscopy, Extended Hückel and MAPLE calculations give strong evidence for the assumption of [InIn₄]⁷⁺ instead of [InIn₄]⁶⁺ and the associated correct composition Na₂₃In₅O₁₅. The problems of a reliable characterization of this unique compound are discussed.     

On Thermodynamic Characteristics of In–I System Compounds

The temperature dependences of the total vapour pressure for solid and liquid InI₂ and liquid InI₃ were measured by the static method with a membran‐gauge manometer. The heat capacities above phases and solid InI₃ were also obtained. The partial pressures In₂I₆, InI₃, InI, In₂I₄, I₂, I were calculated. Absolute entropies and enthalpies of formation InI₂ (crII), InI₂ (l), In₂I₄ (g), InI₃ (l), InI₃ (g), In₂I₆ (g) were obtained. We used the least square method to obtain the mutual consistent sets of data on thermodynamic characteristics of indium iodides in condensed and gaseous phases. The result of this work is the set of standard formation enthalpies and absolute entropies of the In–I system compounds.     

Thermal stability of In2(MoO4)3 and phase equilibria in the MoO3–In2O3 system

Thermal stability of a compound forming in a binary system MoO₃?CIn₂O₃ was investigated by DTA/TG, XRD and SEM methods in this study. For the first time, the diagram of phase equilibria established in the whole range of concentrations of this system's components has been constructed. The temperature and concentration ranges of the components of MoO₃?CIn₂O₃ system in which the compound In₂(MoO₄)₃ co-exists in solid state with MoO₃ or In₂O₃ or with the liquid were determined. The composition and melting point of the eutectic mixture consisting of In₂(MoO₄)₃ and MoO₃ were found.     

Schwache Sn…I‐Wechselwirkungen in den Kristallstrukturen der Iodostannate [SnI4]2– und [SnI3]–

Weak Sn…I Interactions in the Crystal Structures of the Iodostannates [SnI₄]^2– and [SnI₃]^– Iodostannate complexes can be crystallized from SnI₂ solutions in polar organic solvents by precipitation with large counterions. Thereby isolated anions as well as one, two or three‐dimensional polymeric anionic substructures are established, in which SnI₃^– and SnI₄^2– groups are linked by weak Sn…I interactions. Examples are the iodostannates [Me₃N–(CH₂)₂–NMe₃][SnI₄] ( 1 ), (Ph₄P)₂[Sn₂I₆] ( 2 ), [Me₃N–(CH₂)₂–NMe₃][Sn₂I₆] ( 3 ), [Fe(dmf)₆][SnI₃]₂ ( 4 ) and (Pr₄N)[SnI₃] ( 5 ), which have been characterized by single crystal X‐ray diffraction. [Me₃N–(CH₂)₂–NMe₃][SnI₄] ( 1 ): a = 671.6(2), b = 1373.3(4), c = 2046.6(9) pm, V = 1887.7(11) · 10⁶ pm³, space group Pbcm;(Ph₄P)₂[Sn₂I₆] ( 2 ): a = 1168.05(6), b = 717.06(4), c = 3093.40(10) pm, β = 101.202(4)°, V = 2541.6(2) · 10⁶ pm³, space group P2₁/n;[Me₃N–(CH₂)₂–NMe₃][Sn₂I₆] ( 3 ): a = 695.58(4), b = 1748.30(8), c = 987.12(5) pm, β = 92.789(6)°, V = 1199.00(11) · 10⁶ pm³, space group P2₁/c;[Fe(dmf)₆][SnI₃]₂ ( 4 ): a = 884.99(8), b = 1019.04(8), c = 1218.20(8) pm, α = 92.715(7), β = 105.826(7), γ = 98.241(7), V = 1041.7(1) · 10⁶ pm³, space group P1;(Pr₄N)[SnI₃] ( 5 ): a = 912.6(2), b = 1205.1(2), c = 1885.4(3) pm, V = 2073.5(7) · 10⁶ pm³, space group P2₁2₁2₁.     

Die Bildungsenthalpie von SnJ4

The changes of enthalpy for the reactions

1. Sn(c)+2I₂(c)+4165 CS₂(l)=[SnI₄; 4165 CS₂] (sol.),
2. SnI₄(c)+4223 CS₂(l)=[SnI₄; 4223 CS₂] (sol.)

At 298,15 K have been found by solution calorimetry to be ΔH ₁=(?46.7±0.3) and ΔH ₂=(+3.2±0.1) kcal Mol^?1, resp. Neglecting the heat of dilution which is approximately zero these values give ΔH _f ^o (SnI₄; c; 298 K)=9?49.9±0.4) kcal Mol^?1 for the enthalpy of formation of SnI₄. From existing literature data the standard entropy is calculated to beS ^o(SnI₄; c; 298 K)=69,7 cal Mol^?1 K^?1 giving ΔG _f ^o (SnI₄; c; 298 K)=?50,5 kcal Mol^?1 for the corresponding change in theGibbs free energy.     

Two solid phases of pyrimidin‐1‐ium hydrogen chloranilate monohydrate determined at 225 and 120 K

The crystal structures of two solid phases of the title compound, C₄H₅N₂⁺·C₆HCl₂O₄⁻·H₂O, have been determined at 225 and 120 K. In the high‐temperature phase, stable above 198 K, the transition temperature of which has been determined by ³⁵Cl nuclear quadrupole resonance and differential thermal analysis measurements, the three components are held together by O—H...O, N...H...O, C—H...O and C—H...Cl hydrogen bonds, forming a centrosymmetric 2+2+2 aggregate. In the N...H...O hydrogen bond formed between the pyrimidin‐1‐ium cation and the water molecule, the H atom is disordered over two positions, resulting in two states, viz. pyrimidin‐1‐ium–water and pyrimidine–oxonium. In the low‐temperature phase, the title compound crystallizes in the same monoclinic space group and has a similar molecular packing, but the 2+2+2 aggregate loses the centrosymmetry, resulting in a doubling of the unit cell and two crystallographically independent molecules for each component in the asymmetric unit. The H atom in one N...H...O hydrogen bond between the pyrimidin‐1‐ium cation and the water molecule is disordered, while the H atom in the other hydrogen bond is found to be ordered at the N‐atom site with a long N—H distance [1.10 (3) Å].     

Über die Kristallstruktur von In3Mo11O17 sowie über physikalische Eigenschaften oligomerer Oxomolybdate

On the Crystal Structure of In₃Mo₁₁O₁₇ and the Physical Properties of Oligomeric Oxomolybdates In₃Mo₁₁O₁₇ is characterized by its molybdate framework Mo₂₂O₃₄^8? belonging to the general series Mo_4n+2O_6n+4^x? (with n = 5). The phase grows in star-like aggregates and crystallizes within the orthorhombic system (a = 988.0(2) pm, b = 951.2(2) pm, c = 3 176.7(4) pm). There are oligomeric clusters built from five trans edge-sharing Mo₆ octahedra, surrounded by O atoms over all empty edges according to the Aufbau principle Mo₂₂OOO. In the remaining structural channel one finds an In₆⁸⁺ polycation which is geometrically equivalent with the one of In₁₁Mo₄₀O₆₂. The Mo—O and Mo—Mo distances within the cluster are the same like in In₁₁Mo₄₀O₆₂, too, but there are shorter inter cluster distances (306 pm) in In₃Mo₁₁O₁₇. Disorder in the structure may be understood in terms of the presence of constitutional isomers. While the electrical resistivity of PbMo₅O₈ resembles the one of a strongly disturbed metal (with a local minimum around 120 K), the temperature characteristic of Tl_0.8Sn_0.6Mo₇O₁₁ is typical for a semiconductor. Oxomolybdates with even longer oligomers like In₁₁Mo₄₀O₆₂ and In₃Mo₁₁O₁₇ show metallic conductivity. This course corresponds with the sizes of the clusters and their electronic intercoupling which can be estimated from the specific lengths of the inter cluster distances. The effective magnetic moment grows with increasing cluster length from 0.97 μ_B (PbMo₅O₈) to 1.40 μ_B (In₁₁Mo₄₀O₆₂) per cluster (exception: In₃Mo₁₁O₁₂), and so does the contribution of the temperature-independent paramagnetism (from 890 to 2191 × 10^?6$ \frac{{{\rm emu}}}{{{\rm mol}}} $ per cluster). Thus, a single condensed octahedron carries roughly 440 × 10^?6$ \frac{{{\rm emu}}}{{{\rm mol}}} $ as a temperature-independent paramagnetism, similar to the M₆X₁₇ halide clusters. In₁₁Mo₄₀O₆₂ shows an interesting change in the temperature dependence of its magnetic suszeptibility.