[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.     

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.     

Synthese,IR-Spektrum und Kristallstruktur von PPh4[OsCl4(NO)(NSCl)]

Synthesis, I.R. Spectrum, and Crystal Structure of PPh₄[OsCl₄(NO)(NSCl)] Molten trithiazyl chloride reacts with OsCl₃(NO) to yield a product mixture consisting mainly of S₄N₃[OsCl₄(NO)(NSCl)] and S₄N₃Cl. Extraction of this mixture with a solution of tetraphenylphosphonium chloride in dichloromethane affords green (PPh₄)₂[OsCl₅(NO)] · 2 CH₂Cl₂ and the red title compound. PPh₄[OsCl₄(NO)(NSCl)] was characterized by its IR spectrum and an X-ray crystal structure analysis (3001 independent observed reflexions, R = 0.048). Crystal data: monoclinic, space group P2₁/c, Z = 4, a = 1716, b = 1054, c = 1588 pm, β = 96.25°. The compound consists of PPh₄⊕ cations and [OsCl₄(NO)(NSCl)]? anions in which the nitrosyl and the chlorothionitrene ligands have a cis arrangement. Due to positional disorder the NO and NSCl groups are superimposed statistically in the structure model.     

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.     

(PPh4)2[Cl2Re(N3S2)(μ‐NSN)(μ‐N≡ReCl3)]2 – ein Rhenium(VII)‐Komplex mit einer Nitrido‐, einer Dinitridosulfato(II)‐ und einer Rhena‐3,5‐dithia‐2,4,6‐triazino‐Funktion

(PPh₄)₂[Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]₂ – a Rhenium(VII) Complex with a Nitrido, a Dinitridosulfato(II), and a Rhena‐3,5‐dithia‐2,4,6‐triazino Function The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals, which were suitable for a crystal structure determination. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[Cl₂Re^VII(N₃S₂)(μ‐NSN)(μ‐N≡Re^VIICl₃)]₂ ( 1 ): Space group P2₁/c, Z = 2, lattice dimensions at –80 °C: a = 1280.8(2), b = 1017.5(1), c = 2467.8(3) pm, β = 95.04(1)°, R = 0.049. The complex anion of 1 consists of a planar ReN₃S₂‐heterocycle which is connected with the second rhenium atom by a μ‐nitrido bridge as well as by a μ‐dinitridosulfato(II) ligand to form a planar Re₂(N)(NSN) six‐membered heterocycle. This [Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]^– unit dimerizes via one of the N‐atoms of the (NSN)^4– ligand to give a centrosymmetric Re₂N₂ four‐membered ring.     

Die Kristallstrukturen von [ReCl4(PhCCPh)]2 · 2 CH2Cl2 und von PPh4[ReOCl4]

Crystal Structures of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ and PPh₄[ReOCl₄] Single crystals of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ were obtained by chilling dilute solutions of the solvate [ReCl₄(PhC?CPh)POCl₃] in CH₂Cl₂. PPh₄[ReOCl₄] was formed by the reaction of the diphenyl acetylene complex [ReCl₅(PhC?CPh)] with PPh₄Cl · H₂O in CH₂Cl₂ solution. [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂: space group P2₁/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl₂Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh₄[ReOCl₄]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh₄[RuNCl₄] type; it consists of [ReOCl₄]^? anions and PPh₄⁺ cations. The anions are tetragonal with C_4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°.     

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.     

Chlorthionitrenkomplexe des Rheniums Die Kristallstruktur von AsPh4[ReCl4(NSCl)2] · CH2Cl2

Chlorothionitrene Complexes of Rhenium. Crystal Structure of AsPh₄[ReCl₄(NSCl)₂] · CH₂Cl₂ Rhenium pentachloride reacts in POCl₃ solution with (NSCl)₃ forming the chlorothionitrene complexes [(Cl₃PO)ReCl₄(NSCl)] ( I ) and [(Cl₃PO)ReCl₃(NSCl)₂] ( II ). I reacts with AsPh₄Cl in CH₂Cl₂ solution under abstraction of SCl₂ and POCl₃, yielding AsPh₄[ReNCl₄], while II forms the complex AsPh₄[ReCl₄(NSCl)₂] · CH₂Cl₂. The i.r. spectra of the compounds are discussed and assigned. The crystal structure of AsPh₄[ReCl₄(NSCl)₂] · CH₂Cl₂ was determined and refined with X-ray diffraction data (R = 0.031 for 2785 reflexions). It crystallizes in the space group Pī with two formula units per unit cell; the lattice constants are a = 1119, b = 1144, c = 1473 pm, α = 77.6, β = 70.8 and γ = 71.2°. The two NSCl ligands have cis arrangement with nearly linear Re?N?S groups, with interatomic distances corresponding to double bonds. The Re? Cl bonds are somewhat longer than usual and show no trans-effect; this is possibly due to Cl…?H? C bridges.     

Addukte des Oxo-tetrachloro-niobat(V)-Ions Bildung,Schwingungsspektren und Kristallstrukturen von PPh4[NbOCl4(OH2)] und (PPh4)2[NbOCl4(O2PCl2)] · 2 CH2Cl2

Adducts of Oxotetrachloro-niobate (V). Formation, Vibrational Spectra, and Crystal Structures of PPh₄[NbOCl₄(OH₂)] and (PPh₄)₂[NbOCl₄(O₂PCl₂)] · 2 CH₂Cl₂ Crystalline (PPh₄)₂[NbOCl₄(O₂PCl₂)] · 2 CH₂Cl₂ was obtained by hydrolysis of PPh₄[NbSCl₄] in the presence of POCl₃ in CH₂Cl₂. Experiments to obtain the same compound from PPh₄Cl, POCl₃, NbCl₅, and H₂O yielded PPh₄[NbOCl₄(OH₂)]. I.R. spectra of both compounds are discussed. The crystal structure determinations with X-ray diffraction data in both cases show quadratic-pyramidal NbOCl₄^? ions to which a molecule of either H₂O or a PO₂Cl₂^? ion is attached in trans-position to the O atom. PPh₄[NbOCl₄(OH₂)]: tetragonal, space group P4/n, a = 1 308, c = 734 pm, Z = 2, packing as in the AsPh₄[RuNCl₄] type; refinement down to R = 0.046 for 681 reflexions. (PPh₄)₂[NbOCl₄(O₂PCl₂)] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1172, b = 1187, c = 2105 pm, α = 88.40, β = 83.20, γ = 71.28°, Z = 2, packing similar as in (AsPh₄)₂[NbOCl₅] · 2 CH₂Cl₂; refinement to R = 0.059 for 2 502 reflexions.     

Thiokomplexe des Molybdäns Kristallstruktur eines Mischkristalls (PPh3Me)2[Mo2Br6(NO)4]/(PPh3Me)2[Mo2Br6S2(NO)2]

Thiocomplexes of Molybdenum. Crystal Structure of a Mixed Single Crystal (PPh₃Me)₂[Mo₂Br₆(NO)₄]/(PPh₃Me)₂[Mo₂Br₆S₂(NO)₂] The reactions of (PPh₄)₂MoS₄ with MoBr₄ and MoBr₂(NO)₂ resp. lead to the binuclear complexes (PPh₄)₂[S₂MoS₂MoBr₃(SMe₂)] and (PPh₄)[S₂MoS₂MoBr₂(NO)₂], in which the molybdenum atoms are linked by sulfido bridges. The preparation of (PPh₃Me)₂S₆ and (AsPh₄)₂S₇ from Na₂S₄ and PPh₃MeBr, and AsPh₄Cl, respectively, in ethanol solution is described. Disulfido briges are a feature of (AsPh₄)₂[Mo₂Br₆(S₂)₂(SMe₂)₂], which is obtained from MoBr₄(SMe₂)₂ and (AsPh₄)₂S₇. Mixed single crystals containing 2/3 (PPh₃Me)₂[Mo₂Br₆(NO)₄] and 1/3 (PPh₃Me)₂[Mo₂Br₆S₂(NO)₂] are formed in the reaction of MoBr₂(NO)₂ with (PPh₃Me)₂S₆, as shown by X-ray single crystal structure determination. The compound crystallizes monoclinic in the space group C2/c (Internat. Tab. Nr. 15) with four formula units per unit cell (2351 independent observed reflexions, R_w = 0.037). The cell parameters are a = 1603 pm, b = 1549 pm, c = 1863 pm; β = 92.2°. The complexes consist of PPh₃Me^⊕ cations and the dimeric anions [Mo₂Br₆(NO)₄]^2? and [Mo₂Br₆S₂(NO)₂]^2? which occur in the ratio 2:1. In these the molybdenum atoms are connected via MoBr₂Mo bridges of slightly different lengths (Mo? Br 265 pm and 267 pm) forming a controsymmetric double octahedron. All molybdenum atoms have two terminal bromo ligands with Mo? Br bond lengths of 258 pm and 260 pm; in the [Mo₂Br₆(NO)₄]^2? ion each molybdenum has two covalently bonded nitrosyl groups on cis-position with Mo? N bond lengths of 183 pm. In the [Mo₂Br₆S₂(NO)₂]^2? ion one of the two nitrosyl groups at each metal atom is substituted by a terminal sulfido ligand with a Mo? S bond length of 240 pm. The i.r. spectra are reported.     

Cyclothiazenokomplexe von Molybdän(V) und (VI), sowie von Wolfram(VI) Die Kristallstruktur von (PPh4)2[MoCl3(N3S2)]2 · 2 CH2Cl2

Cyclothiazeno Complexes of Molybdenum(V), Molybdenum(VI), and Tungsten(VI). Crystal Structure of (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ . From excess trithiazylchloride and molybdenum or tungsten hexacarbonyl, respectively, the cyclothiazeno complexes [MCl₃(N₃S₂)]₂(S₂N₂) are obtained. They possess metal atoms linked via a planar S₂N₂ ring. The corresponding bromo compounds [MBr₃(N₃S₂)]₂(S₂N₂) can be obtained in liquid bromine from S₄N₄ and MoBr₄ or WBr₆, respectively, or from S₄N₄ with the corresponding metal hexacarbonyls in the presence of bromine. Thermolysis of [WBr₃(N₃S₂)]₂(S₂N₂) yields [WBr₃(N₃S₂)]₂ which is dimerized via nitrogen bridges. When [MoCl₃(N₃S₂)]₂(S₂N₂) reacts with tetraphenylphosphonium chloride in dichloromethane, the S₂N₂ acts as reducing agent, and the paramagnetic molybdenum(V) complex (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ is obtained (μ_eff = 1.2 B.M.). The i.r. spectra are reported. The crystal structure of (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ was determined by X-ray diffraction (2524 independent reflexions, R = 0.052). It crystallizes in the space group P1 with the lattice con- stants a = 943.9, b = 1209.6, c = 1469.2 pm, α = 69.27, β = 72.20 and γ = 82.08°, Z = 1. There are tetraphenylphosphonium cations and centrosymmetric, dimeric anions [MoCl₃(N₃S₂)]₂^2?. The molybdenum atoms are part of six-membered cyclothiazeno rings MoN₃S₂ with MoN bond lengths of 177 and 197 pm; the N atom with the longer MoN bond is linked to the second Mo atom, so that a planar Mo₂N₂ ring results; this ring is nearly coplanar with the two MoN₃S₂ rings. Furthermore, each molybdenum atom is linked with three chlorine atoms with MoCl bond lengths of 240–242 pm, so that the Mo atoms possms a distorted octahedral coordination.     

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.     

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.     

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.     

Chlorthionitrenkomplexe des Wolframs Die Kristallstruktur von [WCl4(NSCl)]2

Chlorothionitrene Complexes of Tungsten. Crystal Structure of [WCl₄(NSCl)]₂ Tungsten hexachloride reacts with trithiazyl chloride, (NSCl)₃, yielding the chlorothionitrene complex [WCl₄(NSCl)]₂, from which AsPh₄[WCl₅(NSCl)] can be obtained by reaction with AsPh₄Cl. Both complexes are characterized by their i.r. spectra. The crystal structure of [WCl₄(NSCl)]₂ was determined and refined with X-ray diffraction data (1059 reflexes, R = 0.055). It crystallizes in the monoclinic space group P2₁/n with the lattice constants a = 1523, b = 904, c = 583 pm and β = 91.35°. In the unit cell there are two centrosymmetric [WCl₄(NSCl)]₂ molecules in which the W atoms are linked via two chloro bridges; short and long W? Cl distances (244 and 265 pm) alternate in the W₂Cl₂ ring, the NSCl groups are found in the trans positions to the longer W? Cl bonds. The WNS bond angle (175°) and short bond distances correspond to a formulation .     

Die Kristallstrukturen von (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN und [ReCl4(18-Krone-6)]

The Crystal Structures of (NH₄)₂[ReCl₆], [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN and [ReCl₄(18)(Crown-6)] Brown single crystals of (NH₄)₂[ReCl₆] are formed by the reaction of NH₄Cl with ReCl₅ in a suspension of diethylether. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN crystallizes as brown crystal plates from a solution of ReCl₅ in acetonitrile. Lustrous green single crystals of [ReCl₄(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl₅ in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH₄)₂[ReCl₆]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH₄)₂[PtCl₆] type, the Re? Cl distance is 235.5(1) pm. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl₂(CH₃CN)₄]⁺ ions with trans chlorine atoms, [ReCl₆]^2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl₄(18-crown-6)]: Space group P2₁/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.     

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.     

Dichloracetylen als stabiler Komplexligand Die Kristallstruktur von PPh4[WCl5(C2Cl2)] · 0,5 CCl4

Dichloro Acetylene as Complex Ligand. Crystal Structure of PPh₄[WCl₅(C₂Cl₂)] · 0.5 CCl₄ Tungsten hexachloride and dichloro acetylenediethyletherate react in boiling CCl₄ in presence of C₂Cl₄ as reducing agent forming [Et₂O · WCl₄(C₂Cl₂)]. In vacuo the complex looses ether giving the dichloro acetylene complex [WCl₄(C₂Cl₂)]₂ which is dimeric with chloro bridges. Both complexes react with tetraphenylphosphonium chloride to form PPh₄[WCl₅(C₂Cl₂)] which is equally prepared by ligand exchange of PPh₄[WCl₅(C₂I₂)] with silver chloride. All dichloro acetylene complexes are red to brown crystalline solids sensitive to moisture, and are thermally and mechanically very stable compared with the highly explosive dichloro acetylene. The compounds are characterized by their i.r. spectra; [Et₂O · WCl₄(C₂Cl₂)] was additionally investigated by ¹³C-nmr spectroscopy. PPh₄[WCl₅(C₂Cl₂)] · 0.5 CCl₄ formes dark brown crystals; according to the structural investigation by X-ray diffraction methods the compound crystallizes orthorhombic in the space group Pbca with 8 formula units per unit cell (1317 observed, independent reflexions, R = 0.049). The cell dimensions are a = 1702 pm, b = 1675 pm and c = 2228 pm. The compound consists of [WCl₅(C₂Cl₂)]? anions and PPh₄⊕ cations including CCl₄ molecules without bonding interactions. The tungsten atoms are seven-coordinated by five chlorine atoms and two carbon atoms. The dichloro acetylene ligand is bonded symmetrically side-on and has a C? C bond length of 128 pm. The W? C distances are 201 pm, the four equatorial Cl atoms have W? Cl bond lengths of 234 pm whereas the chlorine atom in trans-position to the W? C₂ group is situated in a distance of 244 pm.     

Thionitrosylkomplexe des Osmiums. Die Kristallstruktur von AsPh4[OsCl4(NS)2Cl]

Thionitrosyl Complexes of Osmium. Crystal Structure of AsPh₄[OsCl₄(NS)₂Cl] The reaction of osmium pentachloride with trithiazyl chloride (NSCl)₃ yields the thiazylchloride complex [OsCl₄(NSCl)₂], from which the thionitrosyl complex AsPh₄[OsCl₄(NS)₂Cl] is obtained by reaction with AsPh₄Cl in CH₂Cl₂. From this, the neutral thionitrosyl complex [OsCl₄(NS)₂] forms by chloride abstraction with gallium trichloride. The crystal structure of AsPh₄[OsCl₄(NS)₂Cl] was determined and refined with the aid of X-ray diffraction data (R = 0.033, 2161 reflexions). It crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. The lattice constants are a = 1735, b = 1058, c = 1578 pm and β 95.64°. In the [OsCl₄(NS)₂Cl]^? ion the osmium is octahedrally coordinated by four Cl atoms and two NS groups in a cis arrangement. The NS groups are essentially linear with the bond lengths Os?N 184 pm and N?S 146 pm. Loosely attached to one of the S atoms there is a Cl atom (S? Cl distance 228 pm); in the crystal it statistically belongs to both S atoms with an occupation probability of one half, and it cannot be decided whether there is a dynamical fluctuation between the S atoms or a static positional disorder. However, according to the i.r. spectrum the dynamical model seems more probable.     

Azidocuprate(II). Die Kristallstruktur von (PPh4)2[Cu2(N3)6]

Azidocuprates(II). Crystal Structure of (PPh₄)₂[Cu₂(N₃)₆] (PPh₄)₂[Cu(N₃)₄] and (PPh₄)₂[Cu₂(N₃)₆], which is already known, are prepared from the corresponding chloro cuprates and excess silver azide in dichloro methane suspension. The azido cuprates form nonexplosive brown crystals of low sensitivity to moisture and are characterized by i.r. spectroscopy. (PPh₄)₂[Cu₂(N₃)₆] was submitted to a X-ray crystallographic structural analysis (4284 observed, independent reflexions, R = 0.034). The compound crystallizes triclinic in the space group P1 with one formula unit per unit cell. The lattice parameters are a = 1047.4 pm; b = 1131.1 pm; c = 1179.4 pm; α = 101.26°; β = 109.31°; γ = 103.42°. The compound consists of PPh₄^⊕ cations and centrosymmetric anions [Cu₂(N₃)₆]^2?, which meet D_2h-symmetry fairly well. In the anions the copper atoms are linked to a planar Cu₂N₂ four-membered ring by the N α atoms of two azide groups. The other azido ligands are bonded terminally and complete coordination number 4 at the Cu atoms which show planar geometry.