S5N5⊕[GaCl4]⊖ und S5N5⊕[Ga2Cl7]⊖. Synthesen,IR-Spektren und Kristallstrukturen

S₅N₅ ^⊕[GaCl₄]^? and S₅N₅ ^⊕[Ga₂Cl₇]^?. Synthesis, IR Spectra, and Crystal Structures . S₅N₅[GaCl₄] was obtained in high yields from gallium and trithiazyl chloride; depending on the solvent, different second products are formed: S₄N₄Cl[GaCl₄] in dichloromethane and S₃N₂Cl[GaCl₄] in carbon tetrachloride. These products can be separated due to their high solubility in CH₂Cl₂, S₅N₅[GaCl₄] being only slightly soluble. S₃N₂Cl[GaCl₄] can be converted to S₅N₅[GaCl₄] with additional (NSCl)₃. By the action of GaCl₃ on S₅N₅[GaCl₄], S₅N₅[Ga₂Cl₇] is formed. The IR spectra of the title compounds are reported; they differ considerably as well in number as in frequencies of the cation bands and show that the S₅N₅^⊕ ion has different structures depending on the anion. The crystal structures of both compounds were determined by X-ray diffraction. Crystal data: S₅N₅[GaCl₄], orthorhombic, a = 943.8, b = 1369.0, c = 2068.8 pm, space group Pnma, Z = 8 (1381 observed reflexions, R = 0.075); S₅N₅[Ga₂Cl₇], monoclinic, a = 847.5, b = 1298.2, c = 1654.0 pm, β = 93.51°, space group P2₁/n, Z = 4 (1359 observed reflexions, R = 0.065). S₅N₅[GaCl₄] is isotypic with S₅N₅[AlCl₄], showing a heartshaped S₅N₅^⊕ ion, but large ellipsoids of vibration suggest the presence of some kind of disorder (statical or dynamical). In S₅N₅[Ga₂Cl₇] the S₅N₅^⊕ has an azulene-like structure. In both cases the cations are planar, all S? N bond lengths being approximately equal.     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

S4N3⊕[ReCl4(NSCl)2]⊖ Synthese und Kristallstruktur

S₄N₃^⊕[ReCl₄(NSCl)₂]^?. Synthesis and Crystal Structure S₄N₃^⊕[ReCl₄(NSCl)₂]^? is formed as a byproduct in the reaction of Re₂(CO)₁₀ with excess trithiazyl chloride. The compound is characterized by a crystal structure analysis by X-ray methods. S₄N₃[ReCl₄(NSCl)₂] crystallizes in the noncentrosymmetric space group P2₁2₁2₁ with four formula units per unit cell and the lattice dimensions a = 980, b = 1205, c = 1362 pm (2376 observed, independent reflexions; R = 0.076). The compound consists of the well known cyclic planar S₄N₃^⊕-cations and anions [ReCl₄(NSCl)₂]^?, in which the rhenium atom is coordinated octahedral by four Cl atoms and two cis-positioned NSCl ligands. The mean Re? N and N? S bond lengths (177 pm and 158 pm) correspond to double bonds. The bond lengths and angles are much like in the structure of AsPh₄[ReCl₄(NSCl)₂]; however the chlorine atoms of the NSCl ligands are turned to each other.     

Die Schichtstruktur von Tl[CuAsO4] und Tl[CuPO4] mit Zwischenschichten aus Thallium(I) mit stereoaktivem Elektronenpaar

The Layer Structure of Tl[CuAsO₄] and Tl[CuPO₄] with Layers of Thallium(I) with Stereoactive Lone Pair Single crystals of Tl[CuAsO₄] and Tl[CuPO₄] were prepared by reaction of oxygen with Tl/Cu/As and Tl/Cu/P alloys, respectively. The new isotypic compounds crystallize in spacegroup C2/c with Z = 8 and lattice constants a = 684.70(7) pm, b = 712.64(5) pm, c = 1822.4(2) pm, β = 92.76(1)° for Tl[CuAsO₄] and a = 671.57(8) pm, b = 697.09(6) pm, c = 1789.1(2) pm, β = 93.12(1)° for Tl[CuPO₄]. Square planar [CuO₄]-units are connected by common corners to form undulated [CuO₃]₂-chains running along [010]. Interconnection of the chains by arsenate or phosphate groups results in the formation of anionic cuprate-arsenate- and cuprate-phosphate-slabs, respectively. Along [001] these slabs are alternating with double layers of thallium(I) ions in which the stereochemical activity of the Tl⁺ lone pair is apparent from an hemispheric coordination of thallium by oxygen. The structure is related to that of the orthorhombic form of KCuPO₄.     

Synthese und Kristallstruktur von SMe3 ⊕[MoBr4(SMe2)2]−

Synthesis and Crystal Structure of SMe₃^⊕ [MoBr₄(SMe₂)₂]^? . The title compound is obtained from MoBr₄ and excess dimethyl sulfide, forming red crystals which are only slightly sensitive to moisture. Whereas the intermediately formed adduct of MoBr₄ and SMe₂ is unstable, the stable adduct [Mo(NO)₂Br₂(SMe₂)₂] can be prepared from Mo(NO)₂Br₂ and SMe₂. According to the structural analysis by X-ray methods, SMe₃ ^⊕[MoBr₄(SMe₂)₂]^? crystallizes orthorhombic in the space group Imma with eight formula units per unit cell, the cell dimensions being a = 1578, b = 2820, c = 856 pm (1303 observed, independent reflexions). The compound consists of S(CH₃)₃^⊕ cations with S? C bond lengths of 180 pm and C? S? C bond angles of 102° and 103° resp., and anions [MoBr₄(SMe₂)₂]^?. The molybdenum atom is coordinated octahedral by four bromine atoms in equatorial positions and the two S atomes of the SMe₂ donor molecules in axial sites with Mo? S bond lengths of 254 pm.     

Tl5SnF9 und Tl5TiF9: die ersten [Tl5F3]2+‐Schichten in neuartigen Thallium(I)‐fluoridfluorometallaten(IV)

Tl₅SnF₉ and Tl₅TiF₉: The First [Tl₅F₃]²⁺ Layers in Novel Thallium(I) Fluoridefluorometallates(IV) Tl₅TiF₉ and Tl₅SnF₉ were prepared via solid state reactions from mixed powders of the TlF and SnF₄ or TiF₄, respectively, in platinum crucibles under Ar (573 K). Both fluorides are colourless, transparent and extremely hygroscopic. The compounds Tl₅MF₉ (M = Sn, Ti) crystallize in a new structure type in Pbam (Nr. 55) with a = 1117.6 pm, b = 684.8 pm, c = 799.2 pm for Tl₅SnF₉ and a = 1111.4 pm, b = 674.7 pm, c = 783.2 pm for Tl₅TiF₉. Characteristic building units in the new Thallium(I) fluoridefluorometallates(IV) are [Tl₅F₃]²⁺ sheets found for the first time, which are connected via [MF₆]^2– octahedra (M = Ti, Sn) to a threedimensional network (d_Sn–F = 194–197 pm, d_Ti–F = 186–187 pm). The monovalent Tl are coordinated by 8 F with distances Tl–F between 264 and 334 pm. The chemical bonding is discussed on the basis of Extended‐Hückel band structure calculations.     

S5N5⊕[RuCl3(CO)3]⊖ · 0,5 CH2Cl2 Synthese,IR-Spektrum und Kristallstruktur

S₅N₅^⊕[RuCl₃(CO)₃]^⊖ · 0.5 CH₂Cl₂. Synthesis, I.R. Spectrum and Crystal Structure S₅N₅[RuCl₃(CO)₃] · 0.5 CH₂Cl₂ is prepared from Ru₃(CO)₁₂ and trithiazylchloride in boiling dichloromethane; it forms red crystals, which are characterized by it's IR spectrum and by structural determination with X-ray methods. The compound crystallizes monoclinic in the space group C2/c with 8 formula units per unit cell. The lattice dimensions are a = 2047, b = 1064, c = 1637 pm, β = 96.1° (3487 independent, observed reflexions, R = 0.075). The structure consists of planar, cyclic S₅N₅^⊕ cations in the “azulene” conformation with bond lengths SN from 155 to 159 pm, and octahedral [RuCl₃(CO)₃]^⊖ anions with fac-geometry and bond lengths Ru Cl of 242 pm and Ru C of 185 to 190 pm.     

[PPh3Cl]⊕[ReCl4(N2S2)]⊖ Synthese,IR-Spektrum und Kristallstruktur

[PPh₃Cl]^⊕[ReCl₄(N₂S₂)]^?; Synthese, IR-Spektrum und Kristall Strukture The title compound is prepared by the reaction of [ReCl₃(NSCl)₂(POCl₃)] with triphenylphosphane; it formes black crystals. The crystal structure determination was solved with X-ray methods (2861 observed independent reflexions, R = 0.038). The compound crystallizes monoclinic in the space group P2₁/n with four formula units per unit cell. The structure consists of [PPh₃Cl]^⊕ cations and [ReCl₄(N₂S₂)]^? anions, in which the rhenium atom is surrounded octahedrally by four chlorine ligands and the N atoms of a ReN₂S₂-five-membered ring in cis-position (symmetry C_2v). The Re? N bond lengths (181 pm) and the NS bond lengths (152 pm) are in the range of double bonds; the S? S distance is very long (253 pm). The i.r. spectrum is reported.     

Darstellung und elektrochemisches Verhalten von [Nb(OTeF5)6]− und [Ta(OTeF5)6]−-Komplexen

Preparation and Electrochemistry of [Nb(OTeF₅)₆]^? and [Ta(OTeF₅)₆]^? Complexes Nb(OTeF₅)₅ and Ta(OTeF₅)₅ react with Cs[OTeF₅], [Et₄N][OTeF₅], and [(n-Bu)₄N][OTeF₅] to the corresponding Cs[M(OTeF₅)₆], [Et₄N][M(OTeF₅)₆], and [(n-Bu)₄N][M(OTeF₅)₆] complexes, (M = Nb, Ta). The electrochemical reduction of the niobium complex occurs in CH₂Cl₂ at ?0,69 V and in acetonitrile at ?0,60 V (vs. SCE). The tantalum complex is reduced in CH₂Cl₂ at ?1,52 V and in acetonitrile at ?1,42 V (vs. SCE).