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.     

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.     

Reaktionen von Oxiden der Elemente der V. Hauptgruppe mit Trithiazylchlorid Kristallstruktur von (S5N5)4[As8Cl28] · 2 S4N4

Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ Whereas P₄O₁₀ does not react with (NSCl)₃, the oxides As₂O₃, Sb₂O₃, and Bi₂O₃ react under formation of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄, S₅N₅[SbCl₆] and a mixture of S₄N₅[BiCl₄] and S₄N₄Cl[BiCl₄], respectively. The products were characterized by their IR spectra. The crystal structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 2₁c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S₅N₅^⊕ cations, octameric anions [As₈Cl₂₈]^4? and S₄N₄ molecules. The S₅N₅^⊕ ions and the S₄N₄ molecules show positional disorder, which very probably is of dynamical type for the S₅N₅^⊕ ion. The [As₈Cl₂₈]^4? ions can be described as a (so far unknown) [As₄Cl₁₆]^4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl₃ molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.     

Die Reaktionen von Eisen(III)-chlorid mit Trithiazylchlorid. Die Kristallstruktur von [S4N4Cl]+[FeCl4]⊖

Reactions of Iron Trichloride with Trithyazyl Chloride. Crystal Structure of [S₄N₄Cl]⁺[FeCl₄]^? Iron trichloride reacts with (NSCl)₃ yielding S₄N₄[FeCl₄]₂, S₃N₃Cl₂[FeCl₄] or S₄N₄Cl[FeCl₄], depending on the reaction conditions. The i.r. spectra prove the presence of [FeCl₄]^? ions for all three compounds. The ⁵⁷Fe-Mössbauer spectra show a slight quadrupole splitting at 80 K for S₃N₃Cl₂[FeCl₄] (ΔE^Q = 0.42 mm · s^?1) and S₄N₄Cl[FeCl₄] (ΔE^Q = 0.23 mm · s^?1), which indicates a slight deformation of the FeCl₄^? tetrahedra. The crystal structure of S₄N₄Cl[FeCl₄] was determined and refined with X-ray diffraction data (2549 independent reflexions, R = 0.026). S₄N₄Cl[FeCl₄] crystallizes in the triclinic space group P1 with two formula units per unit cell. The lattice constants are a = 712, b = 911, c = 1006 pm, α = 76.5°, β = 83.8° and γ = 80.5°. The structure consists of the so far unknown [S₄N₄Cl]^⊕ cations and slightly deformed FeCl₄^? ions. The [S₄N₄Cl]^⊕ ion consists of a S₄N₄ ring built up of two nearly planar S₃N₂ fragments having a dihedral angle of 136°. The average SN bond length is 157 pm, the SCI bond length 214 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.     

3-Chloro-1,2,3,4-tetraphenylcyclobutenyl-Ennea-chloro-μ-Oxo-di-Niobat(V),[C4Cl(Ph)4]⊕[Nb2OCl9]⊖ Synthese und Kristallstruktur

3-Chloro-1,2,3,4-tetraphenylcyclobutenyl-Ennea-chloro-μ-Oxo-di-Niobate(V), [C₄Cl(Ph)₄]^⊕[Nb₂OCl₉]^?. Synthesis and Crystal Structure The title compound yields from a one step reaction of niobium pentachloride and niobium oxide trichloride with diphenyl acetylene in dichloro methane, forming dark green crystals. The new complex is characterized by the i.r. spectrum and a crystal structure determination by X-ray methods. The compound crystallizes triclinic in the space group P1 with two formula units per unit cell (2253 independent observed reflexions, R = 4.7%). The lattice dimensions are a = 1199, b = 1034, c = 1453 pm; α = 87.0°, β = 108.6°, γ = 96.6°. The cyclobutenyl cation forms an almost planar C₄-ring with two pairs of neighbouring C? C bonds of 139 pm and 153 pm. The anion [Nb₂OCl₉]^? displays a nearly linear NbONb axis (bond angle 174°) in which the NbO bond lengths are 176 pm and 208 pm. Two anions are linked via asymmetric chloro bridges with Nb? Cl bond lengths of 248 pm and 270 pm to form a centrosymmetric dimer.     

Die Reaktion von Trithiazylchlorid mit Titantetrachlorid Die Kristallstruktur von (S4N5)2[Ti2Cl10]

Reaction of Trithiazyl Chloride with Titanium Tetrachloride. Crystal Structure of (S₄N₅)₂[Ti₂Cl₁₀] In the reaction of trithiazyl chloride with titanium tetrachloride, chlorine is abstracted and the brown-yellow adduct TiCl₄(N₂S₂) is obtained. In this compound — according to its i.r. spectrum — a N₂S₂ ring is bonded to the titanium via the N atoms, thus forming a polymer. As a by-product, brown crystalline (S₄N₅)₂[Ti₂Cl₁₀] forms. Its crystal structure was determined and refined with X-ray diffraction data (R = 0.042 for 812 reflexions). It crystallizes in the monoclinic space group P2₁/c with two formula units per unit cell. The lattice constants are a = 670, b = 1 633, c = 1108 pm, β = 97.24°. The structure consists of S₄N₅^⊕ cations, which are nearly equal to those in [S₄N₅]Cl, and [Ti₂Cl₁₀]^2? anions, which are nearly identical with those in (PCl₄)₂[Ti₂Cl₁₀].     

N(SCl)2 ⊕[MoCl5(NSCl)]⊖, ein Chlorthionitrenokomplex von Molybdän(VI)

N(SCl)₂^⊕ [MoCl₅(NSCl)]^?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl₃(N₃S₂) by the reaction of MoCl₄ or MoCl₅ with (NSCl)₃ in CH₂Cl₂. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)₂^⊕[MoCl₅(NSCl)]^? crystallizes in the monoclinic space group P2₁/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl₅(NSCl)]^? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh₄[MoCl₅(NSCl)] are reported.     

CPh3⊕[Ph3CNWCl4(μ-F)WNCl2(μ-F)Cl4WNCPh3]⊖; Synthese und Kristallstruktur eines dreikernigen Nitrido-Nitren-Komplexes des Wolframs

CPh₃^⊕[Ph₃CNWCl₄(μ-F)WNCl₂(μ-F)Cl₄WNCPh₃]^?; Synthesis and Crystal Structure of a Trinuclear Nitrido Nitrene Complex of Tungsten Dark red crystals of the title compound are formed in the reaction of triphenyl carbonium tetrafluoro borate with AsPh₄[WNCl₄] in dichloro methane. They are characterized by a structural analysis by the aid of X-ray diffractional data as well as by it's IR spectrum. The complex crystallizes in the space group P_mmm with two formula units per unit cell. The cell dimensions are a = 2307, b = 1330 and c = 968 pm. Intensity measurements were carried out with 2 255 reflexions. Because of a disorder of the phenyl groups the structural parameters could only be refined to a final R-value of 9.3%. The structure consists of triphenyl carbonium cations and trinuclear anions [WNF₂Cl₂(Cl₄WNCPh₃)₂]^?. The anion can be regarded as a distorded trigonal-bipyramidal ion [WNF₂Cl₂]^?, coordinating to two molecules of Cl₄W?N? CPh₃ in trans-position to the nitrene ligands via W? F…?W bonds with different bond lengths.     

Die Reaktionen von Trithiazylchlorid mit Zirkoniumtetrachlorid Die Kristallstruktur von (S4N4CI)2[Zr2CI10]

Reactions of Zirconium Tetrachloride with Trithiazylchloride. Crystal Structure of (S₄N₄)[Zr₂Cl₁₀] Zirconium tetrachloride reacts with (NSCI)₃ yielding (S₃N₃CI₂)₂[Zr₂CI₁₀], S₄N₄[Zr₂CI₁₀], or (S₄N₄CI)₂[Zr₂CI₁₀], depending of the reaction conditions. These compounds were characterized by their i.r. spectra. They have an ionic structure containing the known ions S₃N₃CI₂⊕, S₄N₄^2⊕, S₄N₄CI^⊕, and the thus far unknown [Zr₂CI₁₀]^2? ion. According to the X-ray structure determination (2827 independent observed reflexions, R = 0.027), (S₄N₄CI)₂[Zr₂CI₁₀] crystallizes in the space group P&1macr; with the lattice constants a = 688, b = 1132, c = 1827 pm, α = 103.2°, β = 98.7° and γ = 91.9⁰ and with Z = 2 formula units per unit cell. The structure is built up from S₄N₄CI^⊕ ions, which are nearly identical as in S₄N₄CI[FeCI₄] and from [Zr₂CI₁₀]^2? ions in which two chloro bridges join two edge-sharing octahedra.     

AsPh4[W2Cl4(N3S2)3] · CCl4; Synthese und Kristallstruktur

AsPh₄[W₂Cl₄(N₃S₂)₃] · CCl₄; Synthesis and Crystal Structure The title compound was obtained in form of black crystals along with other products by the reaction of H₂S and AsPh₄[WCl₄(N₃S₂)] in dichloromethane and subsequent addition of CCl₄. Its crystal structure was determined by X-ray diffraction (3036 observed reflexions, R = 0.051). Crystal data: triclinic, space group P¯1, Z = 2, a = 1369, b = 1398, c = 1441 pm, α = 64.8, β = 68.02 and γ = 58.1°. The compound consists of AsPh₄^⊕ ions, CCl₄ molecules and [W₂Cl₄(N₃S₂)₃]^? ions. In the latter, one tungsten atom is member of one planar WN₃S₂ ring while the second tungsten atom belongs to two such rings forming a nearly planar S₂N₃WN₃S₂ unit. Two nitrogen atoms of this unit are linked to the other tungsten atom forming a WN₂W ring. Two chloro ligands at each tungsten atom complete the coordination sphere to coordination numbers of six.     

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.     

Komplexe des Rheniums mit planarer ReN2S2-Fünfringstruktur Synthesen und Kristallstrukturen von AsPh4[ReCl4(N2S2)] und PPh4[ReBr4(N2S2)]

Complexes of Rhenium with Planar ReN₂S₂ Rings. Syntheses and Crystal Structures of AsPh₄[ReCl₄(N₂S₂)] and PPh₄[ReBr₄(N₂S₂)] The complex [ReCl₄(N₂S₂)]^? can be obtained as PPh₄^⊕ or AsPh₄^⊕ salt by the action of S(NSiMe₃)₂ and of diphenylacetylene, respectively, on the chlorothionitrene complex [ReCl₄(NSCl)₂]^?. Another method of synthesis is the reaction of [ReCl₃(NSCl)₂(POCl₃)] with SbPh₃. [ReBr₃(N₂S₂)]₂ is obtained from excess Me₃SiBr and [ReCl₃(NSCl)₂(POCl₃)]. The anionic complex [ReBr₄(N₂S₂)]^? forms from either [ReCl₄(NSCl)₂]^? or [ReCl₄(N₂S₂)]^? with Me₃SiBr. All compounds are black, diamagnetic, and sensitive to moisture; the PPh₄^⊕ and AsPh₄^⊕ salts are soluble in CH₂Cl₂ and CH₂Br₂. The IR spectra are reported. The crystal structures of AsPh,₄[ReCl₄(N₂S₂)] and PPh₄[ReBr₄(N₂S₂)] were determined by X-ray diffraction. AsPh₄[ReCl₄(N₂S₂)]: space group P2/n, Z = 2, a = 1244.5, b = 1429.3, c = 791.1 pm, γ = 96.89° (1715 observed reflexions, R = 0.082). PPh₄[ReBr₄[ReBr₄(N₂S₂)]: space group P2₁/n, Z = 4, a = 961.7, b = 1397.4, c = 2205.7 pm, β = 102.10° (1787 observed reflexions, R = 0.073). In both compounds the [ReX₄(N₂S₂)]? anions have the same type of structure, the Re atoms forming part of planar ReN₂S₂ rings; the bond lengths are ReN 177 pm, NS 152 pm, and SS 259 for the chloro compound and ReN 184 pm, NS 153 pm, and SS 264 pm for the bromo compound. In AsPh₄[ReCl₄(N₂S₂)] the cations are stacked to form columns in the c-direction; in PPh₄[ReBr₄(N₂S₂)], there is considerable distortion form this packing principle.     

Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Formation of PPh₄[WOCl₄ · THF] and PPh₄Cl · 4As₄S₃ from W(CO)₆ and PPh₄[As₂SCl₅] and their Crystal Structures When W(CO)₆ and PPh₄[As₂SCl₅] are irradiated with UV light in tetrahydrofurane, PPh₄[WOCl₄ · THF], PPh₄ Cl· 4As₄S₃ and PPh₄[Cl₂H] are obtained. X-ray crystal structure determinations were performed. PPh₄[WOCl₄ · THF], monoclinic, space group P2₁/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh₄⁺ and [WOCl₄. THF]^? ions are present, the WOCl₄ group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh₄Cl · 4AsS₃, tetragonal, I4₁/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh₄⁺ and Cl^? ions and As₄S₃ molecules.     

Thiohalogeno-Verbindungen von Niob und Tantal: NbSCl3, TaSCl3, [NbSCl5]2−, [TaSCl5]2−, [NbSBr4]− Die Kristallstrukturen von (PPh4)2[NbSCl5] · 2 CH2Cl2 und NEt4[NbCl6]

Thiohalo Compounds of Niobium and Tantalum: NbSCl₃, TaSCl₃, [NbSCl₅]^2?, [TaSCl₅]^2?, [NbSBr₄]^?. Crystal Structures of (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ and NEt₄[NbCl₆] NbSCl₃ can be obtained from NbCl₅ by reaction with H₂S or bistrimethylsilyl sulfide in a suspension of CCl₄ or CH₂Cl₂, respectively; in the latter case the product contains a rest of trimethylsilyl groups. This also applies for TaSCl₃, NbSBr₃ and TaSBr₃, which are formed from the metal pentahalides and S(SiMe₃)₂. NEt₄[NbSCl₄] is formed together with NEt₄[NbCl₆] in the reaction of NbCl₅ with NEt₄SH in CH₂Cl₂. PPh₄[NbCl₆] reacts with S(SiMe₃)₂ in dichloromethane yielding (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂, whereas PPh₄[NbSBr₄] is obtained from PPh₄[NbBr₆] and S(SiMe₃) under the same conditions. (PPh₄)₂[TaSCl₅] · 2 CH₂Cl₂ was obtained from TaSCl₃ and PPh₄Cl in CH₂Cl₂. According to an X-ray crystal structure determination (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ crystallizes in the β-(AsPh₄)₂[UCl₆] · 2 CH₂Cl₂ type with positionally disordered, octahedral anions. Crystal data: a = 1 021.7, b = 1120.4, c = 1 243.3 pm, α = 70.77, β = 80.24, γ = 80.54°, space group P1 , Z = 2; 2462 unique observed reflexions, R = 0.036. NEt₄[NbCl₆] crystallizes isotypic to NEt₄[WCl₆], a = 723.5, b = 1 018.0, c = 1 174.6 pm, β = 100.07°, space group P2₁/n, Z = 2; 1 875 reflexions, R = 0.075.     

(PPh4)2[MoN(N3)3Cl]2; Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[MoN(N₃)₃Cl]₂; Synthesis, IR Spectrum, and Crystal Structure The title compound is formed in the reaction of molybdenum (II) benzoate with trimethylsilyl azide and PPh₄Cl in dichloro methane forming dark red single crystals. A PPh₃Me⊕ salt of the ion [MoN(N₃)₃Cl]₂^2? is obtained from (PPh₃Me)₂MoNCl₄] treated with silver azide in CH₂Cl₂ suspension. The solvent CH₂Cl₂ participates in both reactions as oxidizing agent. (PPh₄)₂[MoN(N₃)₃Cl₂ is characterized by a structural analysis based upon X-ray data: space group P1 , Z = 1, a = 1050.7 pm; b = 1185.4 pm; c = 1190.8 pm; α = 98.90°; β = 106.87°; γ = 103.97° (4505 independent, observed reflexions, R = 0.039). The compound consists of PPh₄⊕ cations and centrosymmetric anions [MoN(N₃)₃Cl₂^2? in which the molybdenum atoms are bridged by the N_α atoms of two azide groups; the resulting Mo? N bond lengths are 208 pm and 260 pm. In trans position to the long Mo? N bond the terminal nitrido ligand is situated, the Mo?N distance of 164 pm corresponds to a triple bond. Two terminal azido ligands and the chloro ligand are filling up the coordination sphere of the molybdenum atoms to a coordination number of six. The i.r. spectrum is reported and assigned.     

Pentabromothio-diarsenat und -diantimonat: Darstellung,Schwingungsspektren und Kristallstrukturen von PPh4[As2SBr5] und PPh4[Sb2SBr5]

Pentabromothio-diarsenate and -diantimonate: Preparation, Vibrational Spectra, and Crystal Structures of PPh₄[As₂SBr₅] and PPh₄[Sb₂SBr₅] The title compounds were obtained in CH₂Br₂ from PPh₄Br, HBr and As₂S₃ or Sb₂S₃, respectively. Their i.r. and Raman spectra are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh₄[As₂SBr₅], monoclinic, space group P2₁/n, Z = 4, a = 1192.3, b = 1528.1, c = 1618.0 pm, β = 95.53°, isotypic with PPh₄[As₂SCl₅] (structure determination with 1539 observed reflexions, R = 0.052); PPh₄[Sb₂SBr₅], triclinic, space group P1 , Z = 2, a = 1044,8, b = 1207.1, c = 1307.8 pm, α = 104.77, β = 108.63, γ = 98.34° (2398 observed reflexions, R = 0.032). Both ions, [As₂SBr₅]^? and [Sb₂SBr₅]^?, have the same general structure: including the lone electron pairs, the As and Sb atoms have distorted trigonal-bipyrimidal coordination, two bipyramids sharing a common edge with sulfur and bromine as bridging atoms. The [As₂SBr₅]^? ions are associated to chains via As…Br contacts, the [Sb₂SBr₅]^? ions form pseudodimeric units by Sb…S and Sb…Br contacts. Whereas the crystal packing of the As compound is similar to that of other PPh₄⁺ compounds having a cation to anion ratio of 1:1, the Sb compound shows the packing principle known for 2:1 compounds.     

Zur Chemie der Chlorthionitrenkomplexe des Rheniums Die Kristallstruktur von [N(SCl)2]⊕ [Re2Cl9]⊖

Chemistry of Chlorothionitrene Complexes of Rhenium. Crystal Structure of [N(SCl)₂]⊕ [Re₂Cl₉]? By reaction of S₃N₂Cl₂ with ReCl₅ the chlorothionitrene complex [ReCl₃(NSCl)₂]₂ is obtained in good yield; it has a dimer structure with chloro bridges. By the same reaction in POCl₃ solution the solvate [ReCl₃(NSCl)₂OPCl₃] is obtained. Instead, when a molar ratio of ReCl₅ and S₃N₂Cl₂ of 2:1 is taken, the product is [N(SCl)₂][Re₂Cl₉]. [ReCl₄(NSCl)OPCl₃] and excess PPh₃ react to give the nitrido complex [ReNCl₂(PPh₃)₂]. The crystal structure of [N(SCl)₂][Re₂Cl₉] was determined and refined with X-ray diffraction data (1021 independent reflexions, R = 0.031). It crystalizes in the space group C2/c with four formula units per unit cell (a = 1197, b = 1288, c = 1144 pm, ß = 107.83°). The [N(SCl)₂]⊕ cations have exactly C₂ and approximately C_2v symmetry; the NS bond lengths of 162 pm and the bond angles SNS (133.6°) and NSCl (117.6°) deviate considerably from the values of known [N(SCl)₂]⊕ structures. The [Re₂Cl₉]? anion consists of two face sharing octahedra and has a Re—Re distance of 270 pm. I. r. spectra of all compounds are reported and discussed.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Thiochloro-Verbindungen von fünfwertigem Niob und Wolfram: WSCl3, [WSCl4]22−, [NbSCl4]− Die Kristallstruktur von PPh4[NbSCl4]

Thio-chloro Compounds of Pentavalent Niobium and Tungsten: WSCl₃, [WSCl₄]₂^2?, [WSCl₅]^2?, [NbSCl₄]^?. Crystal Structure of PPh₄[NbSCl₄] Black WSCl₃ was obtained by reduction of (WSCl₄)₂ with C₂Cl₄. With PPh₄Cl in CH₂Cl₂ it yields (PPh₄)₂[WSCl₄]₂ which has a dimeric structure with chloro bridges according to its i. r. spectrum. Iodide reduces PPh₃Me[WSCl₅] in CH₂Cl₂ to (PPh₃Me)₂[WSCl₅], from which (PPh₃Me)₂[WSBr₅ · BBr₃] is obtained by reaction with BBr₃. From PPh₄Cl in CH₂Cl₂ and raw NbSCl₃ (obtained by solid state reaction of NbCl₅ with B₂S₃) PPh₄[NbSCl₄] is formed. The crystal structure of PPh₄-[NbSCl₄] was determined and refined with X-ray diffraction data (residual index R = 0.066 for 1017 reflexions). It crystallizes in the AsPh₄[RuNCl₄] structure type (space group P4/n) with the lattice constants a = 1303 and c = 760 pm. The quadratic-pyramidal [NbSCl₄]^? ion has a Nb?S bond length of 209 pm. The i. r. spectra of all compounds are discussed.