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.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

Reaktionen von Uranpentabromid Die Kristallstrukturen von PPh4[UBr6], PPh4 [UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN und (PPh4)2[UO2Br4] · 2CH2Cl2

Reactions of Uranium Pentabromide. Crystal Structures of PPh₄[UBr₆], PPh₄[UBr₆] · 2CCl₄, (PPh₄)₂[UBr₆] · 4CH₃CN, and (PPh₄)₂[UO₂Br₄] · 2CH₂Cl₂ PPh₄[UBr₆] and PPh₄[UBr₆] · 2CCl₄ were obtained from UBr₅ · CH₃CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl₄. Their crystal structures were determined by X-ray diffraction. PPh₄[UBr₆]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh₄[UBr₆] · 2CCl₄: 2973 reflexions, R = 0.074, space group P2₁/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr₅ with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr₄ · CH₃CN and UBr₄ · 3CH₃CN, respectively. These react with PPh₄Br in acetonitrile affording (PPh₄)₂[UBr₆] · 4CH₃CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P2₁/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt₄)₂[U₂Br₁₀] was obtained; (PPh₄)₂[U₂Br₁₀] formed from UBr₄ and PPh₄Br in CH₂Cl₂. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh₄)₂[U0₂Br₄]· 2 CH₂Cl₂, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr₆-, 276.7 pm for UBr₆^2? and 282.5 pm for UO₂Br₄^2?     

Die Kristallstrukturen von (Ph4P)2[HfCl6]·2CH2Cl2 und (Ph4P)2[Hf2Cl10]·CH2Cl2

Crystal Structures of (Ph₄P)₂[HfCl₆]·2CH₂Cl₂ and (Ph₄P)₂[Hf₂Cl₁₀]·CH₂Cl₂ Colourless single crystals of (Ph₄P)₂[HfCl₆]·2CH₂Cl₂ ( 1 ) and (Ph₄P)₂[Hf₂Cl₁₀]·CH₂Cl₂ ( 2 ) were obtained from hafniumtetrachloride and tetraphenylphosphonium chloride in dichloromethane solution, using the corresponding stoichiometry of the educts. Both compounds were characterized by X‐ray structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1018.3(1), b = 1121.0(1), c = 1240.1(1) pm, α = 70.55(1)°, β = 81.38(1)°, γ = 80.02(1)°, R₁ = 0.0374. 2 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1124.4(1), b = 1141.9(1), c = 1281.4(1) pm, α = 63.80(1)°, β = 68.15(1)°, γ = 86.33(1)°, R₁ = 0.0208.     

Die Komplexbildung von 4-(2-Thiazolazo)-resorcin mit Kupfer(II), Blei(II), Zink(II), Cadmium(II) und Wismut(III)

Ohne Zusammenfassung     

Thiobromokomplexe von Arsen und Antimon Darstellung und Kristallstrukturen von (PPh4)2[As2SBr6] · CH2Br2 und (PPh4)2[Sb2SBr6] · CH2Br2

Thiobromo Complexes of Arsenic and Antimony. Preparation and Crystal Structures of (PPh₄)₂[As₂SBr₆] · CH₂Br₂ and (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂ (PPh₄)₂[As₂SBr₆] · CH₂Br₂ is formed by the reaction of As₂S₃, PPh₄I and HI in dibromomethane. It can also be obtained, as well as (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂, from (PPh₄)₂[As₂Br₈] and (PPh₄)₃[Sb₂Br₉], respectively, with bistrimethylsilylsulfide. The crystal structures of the title compounds were determined by X-ray diffraction. They are isotypic with (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂. In the anions [M₂SBr₆]^2? the M atoms (As or Sb) have a distorted octahedral coordination, the two octahedra share acommon face with one bridging S and two Br atoms; the lone electron pairs occupy the trans positions to the S atom. Crystal data: triclinic, space group P1 , Z = 2; (PPh₄)₂[As₂SBr₆] · CH₂Br₂, a = 119.1, b = 1203.6, c = 2067.5 pm α= 94.89, β = 97.78, γ = 112.20°, 3046 independent observed reflexions, R = 0.083; (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂, a = 1198.9, b = 1224.3, c = 2085.5pm, α = 95.04, β = 98.48, γ = 112.13°C, 2380 reflexions, R = 0.079.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Die Kristallstrukturen von [Cu2Cl2(AA · H+)2](NO3)2 und [AA · H+]Pikr− (AA · H+ = Allylammonium; Pikr− = Pikrat)

The Crystal Structures of [Cu₂Cl₂(AA · H⁺)₂](NO₃)₂ and [AA · H⁺]Picr^? (AA · H⁺ = Allylammonium; Picr^? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu₂Cl₂(AA · H⁺)₂](NO₃)₂ has been obtained from CuCl₂ · 2H₂O, allylamine (AA), and HNO₃ in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P2₁/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of Cu_nCl_n chains which are connected by π-bonding bidentate AA · H⁺ …? ON(O)O …? H⁺ · AA units. For comparision with the above complex the structure of [AA · H⁺]Picr^? (Picr^? = picrate anion) is also reported.     

4-Methyl-1,2,3,5-dithiadiazoliumsalze Die Kristallstrukturen von (CH3CN2S2)5[CoCl4]Cl3 und (CH3CN2S2)Cl

4-Methyl-1,2,3,5-dithiadiazolium Salts. Crystal Structures of(CH₃CN₂S₂)₅[CoCl₄]Cl₃ and (CH₃CN₂S₂)Cl 4-Methyl-1,2,3,5-dithiadiazolium tetrachlorocobaltate trichloride, (CH₃CN₂S₂)₅[CoCl₄]Cl₃, was obtained by reaction of trithiazyl chloride, (NSCl)₃, with CoCl₂ in acetonitrile; it forms brown, moisture sensitive crystals. With tetraphenylarsonium chloride in CH₂Cl₂ it yields yellow crystalline (CH₃CN₂S₂)Cl and (AsPh₄)₂CoCl₄. The IR spectra of the title compounds are reported and assigned. Theit crystal structures were determined by X-ray diffraction. Crystal data: (CH₃CN₂S₂)₅[CoCl₄]Cl₃, orthorhombic, P2₁2₁2₁, Z = 4, a = 830, b = 1603, c = 2443 pm at 180 K (structure determination with 1787 observed independent reflexions, R = 0.070); (CH₃CN₂S₂)Cl, triclinic, P2₁2₁2₁, Z = 4, a = 749, b = 819, c = 1015 pm, α = 84.9, β = 67.4, γ = 84.6° at 296 K (2653 reflexions, R = 0.040). Both compounds are ionic, having chloride and distorted tetrahedral CoCl₄^2? anions and planar 4-methyl-1,2,3,5-dithiadiazolium cations which nearly fulfill C_2v symmetry. The (CH₃CN₂S₂)₅[CoCl₄]Cl₃ structure contains five symmetry independent cations, (CH₃CN₂Cl has two symmetry independent cations, all being nearly equal. No nitrogen atom but all sulfur atoms of the cations have contact with three to five chlorine atoms, and as a rule there is one chloride ion which is coplanar with the cation and exhibits rather short distances to both S atoms (288 to 309 pm); therefore, the positive charge of the cations must be concentrated on the sulfur atoms.     

Darstellung und Kristallstrukturen von Ag[N(CN)2](PPh3)2, Cu[N(CN)2](PPh3)2 und Ag[N(CN)2](PPh3)3

Preparation and Crystal Structures of Ag[N(CN)₂](PPh₃)₂, Cu[N(CN)₂](PPh₃)₂, and Ag[N(CN)₂](PPh₃)₃ The coordination compounds Ag[N(CN)₂](PPh₃)₂ ( 1 ), Cu[N(CN)₂](PPh₃)₂ ( 2 ), and Ag[N(CN)₂](PPh₃)₃ ( 3 ) are obtained by the reaction of AgN(CN)₂ or CuN(CN)₂ with triphenylphosphane in CH₂Cl₂. X‐ray structure determinations were performed on single crystals of 1 , 2 , and 3 · C₆H₅Cl. The three compounds crystallize monoclinic in the space group P2₁/n with the following unit cell parameters. 1 : a = 1216.07(9), b = 1299.5(2), c = 2148.4(3) pm, β = 99.689(13)°, Z = 4; 2 : a = 1369.22(10), b = 1257.29(5), c = 1888.04(15) pm, β = 94.395(7)°, Z = 4; 3 · C₆H₅Cl: a = 1276.6(4), b = 1971.7(3), c = 2141.3(5) pm, β = 98.50(3)°, Z = 4. In all structures the metal atoms have a distorted tetrahedral coordination. The crystal structure of 3 · C₆H₅Cl shows monomeric molecular units with terminal coordinated dicyanamide. The crystal structure of 1 is built up by dinuclear units, which are bridged by dicyanamide ligands. However, the crystal structure of 2 corresponds to a onedimensional coordination polymer, bridged by dicyanamide anions.     

Synthese und Kristallstrukturen von (PPh4)2[TeS3] · 2 CH3CN und (PPh4)2[Te(S5)2]

Synthesis and Crystal Structures of (PPh₄)₂[TeS₃] · 2 CH₃CN and (PPh₄)₂[Te(S₅)₂] (PPh₄)₂[TeS₃] · 2 CH₃CN was obtained by the reaction of PPh₄Cl, Na₂S₄ and Te in acetonitrile. With sulfur it reacts yielding (PPh₄)₂[Te(S₅)₂]. The crystal structures of both products were determined by X-ray diffraction. (PPh₄)₂[TeS₃] · 2 CH₃CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS₃]^2? ions with an average Te? S bond length of 233 pm. (PPh₃)₂[Te(S₅)₂]: monoclinic, P2₁/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S₅)₂]^2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S₅ groups forms a ring with chair conformation.     

Die Kristallstruktur von BaHg(CN)4 · 4 Pyridin

Crystal Structure of BaHg(CN)₄ · 4 Pyridine The structure of the tetragonal BaHg(CN)₄ · 4 Pyridine (space group I4 , a = 1119.4(7), c = 1 057.9(7) pm, Z = 2, d_c = 1.87 g · cm^?3) contains tetrahedral Hg(CN)₄ and bisdisphenoide Ba(NC)₄(py)₄ groups, which are linked together by Hg? CN? Ba bridges. The BaHg(CN)₄ framework consists of a 3-dimensional network of all round edge-sharing tetrahedrons. The analogous strontium compound is isotype with a = 1 108.2(9) and c = 1 035.3(14) pm.     

Synthese und Kristallstrukturen der Polyselenidokomplexe (PPh4)6[M(Se4)2]2[WSe4] · DMF mit M = Zink und Quecksilber

Syntheses and Crystal Structures of the Polyselenido Complexes (PPh₄)₆[M(Se₄)₂]₂[WSe₄] · DMF with M = Zinc and Mercury The title compounds have been prepared by the reactions of the acetates of zinc and mercury, respectively, with excess (PPh₄)₂ WSe₄ in boiling dimethylformamide, forming black-red single crystals. According to the X-ray structure determinations both compounds crystallize isotypically in the space group 12/a with four formula units per unit cell. (PPh₄)₆[Zn(Se₄)₂]₂[WSe₄] · DMF: a = 2888.1(6), b = 1740.3(2), c = 2893.9(4) pm, β = 90.47(1)°. 3230 observed unique reflections, R = 0.009. (PPh₄)₆[Hg(Se₄)₂]₂[WSe₄] · DMF: a = 2891.8(5), b = 1738.0(4), c = 2920.1(5) pm, β = 90.29(2)°. 2978 observed unique reflections, R = 0.115%. The compounds consist of PPh₄⁺ ions, spirocyclic octaseleno metallates [M(Se₄)₂]^2?, tetrahedral WSe₄²-ions, and disordered DMF Molecules.     

Thiochlorowolframate von Wolfram(V) und -(VI). Die Kristallstrukturen von PPh4[WSCl4] und (PPh4)2[WS2Cl4] · 2 CH2Cl2

Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ Diamagnetic (NEt₄)₂[WSCl₄]₂, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl₅ with NEt₄SH as well as by the reduction of WSCl₄ with NEt₄I in dichloromethane. If the reduction is performed with PPh₄I, PPh₄[WSCl₄] with monomer anions is formed. Reaction of WCl₆ with H₂S in dichloromethane yields brown, insoluble WS₂Cl₂ which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS₂Cl₂ and PPh₄Cl react to afford PPh₄[WS₂Cl₃] · 2 CH₂Cl₂ and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂. IR spectra are reported. The crystal structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ were determined by X-ray diffraction. PPh₄[WSCl₄]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl₄]^? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS₂Cl₄]^2? has cis configuration; as it is situated on an inversion center it shows positional disorder.     

Phosphaniminato-Komplexe von Titan(IV) und Titan(III). Die Kristallstrukturen von [TiCl2(OMe)(NPPh3)]2, [TiBr2(NPPh3)]2 · 3 C7H8 sowie von [Ph3PNH2]Br · CH2Cl2

Phosphorane Iminato Complexes of Titanium(IV) and Titanium(III). The Crystal Structures of [TiCl₂(OMe)(NPPh₃)]₂, [TiBr₂(NPPh₃)]₂ · 3C₇H₈, and [Ph₃PNH₂]Br · CH₂Cl₂ TiCl₃(NPPh₃) reacts with a solution of methyllithium in diethyl ether in the presence of lithiummethylate forming yellow [TiCl₂(OMe)(NPPh₃)]₂. On reaction with benzyl magnesium bromide TiCl₃(NPPh₃) in diethyl ether is converted into green [TiBr₂(NPPh₃)]₂ under reduction and ligand exchange. [TiBr₂(NPPh₃)]₂ crystallizes from toluene with three molecules C₇H₈. [Ph₃PNH₂]Br · CH₂Cl₂ originates as a side product of this reaction. The products are characterized by their i.r. spectra and by crystal structure analyses. [TiCl₂(OMe)(NPPh₃)]₂ . Space group P1 , Z = 2, structure solution with 2909 independent reflections, R = 0.063. Lattice dimensions at 20°C: a = 1005.1, b = 1044.5, c = 1068.6 pm, α = 66.98°, β = 89.35°, γ = 80.24°. The compound forms centrosymmetric dimeric molecules with μ₂-OMe bridges and five-fold coordinated titanium atoms. The (NPPh₃^?) ligand is terminally connected with a Ti = N distance of 174.8 pm and with a TiNP bond angle of 165.3°. [TiBr₂(NPPh₃)]₂ · 3 C₇H₈ . Space group P1 , Z = 2, structure solution with 5548 independent reflections, R = 0.053. Lattice dimensions at ?70°C: a = 983.3, b = 1162.7, c = 1376.5 pm, α = 100.53°, β = 110.30°, γ = 105.24°. The compound forms centrosymmetric dimeric molecules with μ₂-NPPh₃ bridges and tetrahedral coordination at the titanium atoms. With 195.9 pm the Ti–N bonds correspond with single bonds. The Ti …? Ti distance of 260.0 pm is exceptionally short. [Ph₃PNH₂]Br · CH₂Cl₂ . Space group P1 , Z = 1, structure solution with 3091 independent reflections, R = 0.049. Lattice dimensions at 20°C: a = 909.4, b = 1004.4, c = 1158.5 pm, α = 108.09°, β = 94.67°, γ = 91.92°. The bromide ions are bonded to a one-dimensional infinite network via hydrogen bridge bonds of the cation and of the dichloromethane.     

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.     

Phosphaniminato-Komplexe von Cobalt und Zink mit Heterocubanstruktur. Die Kristallstrukturen von [CoI(NPMe3)]4 und [ZnI(NPMe3)]4

Phosphoraneiminato Complexes of Cobalt and Zinc with Heterocubane Structure. Crystal Structures of [CoI(NPMe₃)]₄ and [ZnI(NPMe₃)]₄ The title compounds have been prepared from CoI₂ and ZnI₂, respectively, and Me₃SiNPMe₃ by fusion reactions at 180°C in the presence of sodium fluoride. They crystallize from dichloromethane as dark green (Co) or colourless (Zn) single crystals including three molecules CH₂Cl₂ per formula unit, which were characterized by crystal structure determinations. [CoI(NPMe₃)]₄ · 3 CH₂Cl₂: Space group P3m1, Z = 2, structure solution with 2376 independent reflections, R = 0.033. Lattice dimensions at ?50°C: a = b = 1455.8, c = 1270.5 pm. [ZnI(NPMe₃)]₄ · 3 CH₂Cl₂: Space group P3m1, Z = 2, structure solution with 2197 independent reflections, R = 0.043. Lattice dimensions at ?60°C: a = b = 1454.9, c = 1270.5 pm. Both complexes are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ₃-N-bridges of the phosphoraneiminato groups with M₄N₄ bridge-type bond angles close to 90°.