Halogeno-Nitrosylkomplexe von Molybdän und Wolfram. Die Kristallstrukturen von [Na2(15-Krone-5)2(CH3CN)][MoCl4(NO)2] und [Na(15-Krone-5)]2[MoF4Cl(NO)]

Halogeno-Nitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of [Na₂(15-Crown-5)₂(CH₃CN)][MoCl₄(NO)₂] and [Na(15-Crown-5)]₂[MoF₄Cl(NO)] MoCl₂(NO)₂ and WCl₂(NO)₂, respectively, react with excess sodium fluoride in acetonitrile at room temperature and in the presence of 15-crown-5 to give crystalline mixtures, which consist of the title compounds, respectively of [Na(15-crown-5)]₂[WCl₄(NO)₂] and [Na(15-crown-5)]₂[WF₄Cl(NO)], and which can be separated by selection. The complexes are characterized by their i.r. spectra, the molybdenum compounds additionally by crystal structure determinations. [Na₂(15-crown-5)₂(CH₃CN)][MoCl₄(NO)₂]: Space group P2₁, Z = 2, 5415 independent unique reflexions, R = 0.039. Lattice dimensions at ?10°C: a = 984.3, b = 1231.1, c = 1483.0 pm, β = 105.67°. The compound consists of cations [Ne(l5-crown-5)(CH₃CN)]⁺, in which the sodium ion is surrounded by the five O-atoms of the crown ether and by the N-atom of the acetonitrile molecule, as well as of anions, which form an ion pair {Na(15-crown-5)[MoCl₄(NO)₂]}^?. In the in pairs the sodium ion is coordinated by the five oxygen atoms of the crown ether and by two chlorine atoms of the [MoCI₄(NO)₂]^2? unit. The nitrosyl ligands take the cis-position a t the molybdenum atom which is in a distorted octahedrally fashion. [Na(15-crown-5)]₂[MoF₄Cl(NO)]. Space group C2/c, Z = 4, 1933 independent unique reflexions, R = 0.078. Lattice dimensions at ?7O°C: D : 1.585.8, b = 1171.5, c = 1771.5 pm, β = 114.91°. The compound forms an ion triple, in which the sodium ions are linked to five oxygen atoms each of the crown ether molecules, and to two F-atoms of the [MoF₄Cl(NO)]^2? unit. The F-atom which is arranged in trans-position to the nitrosyl ligand coordinates with both sodium ions; thus an unusual T-shaped arrangement results for this F-atom. The sole terminal F-Atom and the Cl-atom are disordered in two positions.     

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.     

Synthese und Kristallstruktur des Nitridokomplexes [Na-15-Krone-5]2[MoNF4]2 · 2 CH3CN

Synthesis and Crystal Structure of the Nitrido Complex [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN The title compound is synthesized by the reaction of [MoCl₄(NSCl)]₂ with excess NaF in boiling acetonitrile in the presence of the crown ether 15-crown-5. [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN forms yellow crystals, which were characterized by an X-ray structure determination. Space group P1 , Z = 1. Lattice dimensions at ?90°C: a = 855.5, b = 1 069.9, C = 1 143.5 pm, α = 105.71°, β = 95.29°, γ = 102.25° (4 096 independent observed reflexions, R = 0.039). Short Na…?F contacts of 234 pm with the four axial fluoro ligands of the dimeric anion [MoNF₄]₂^2? allow formulation of a triple ion. The centrosymmetric anion is dimerized by bent fluoro bridges with Mo? F distances of 198 and 245 pm. The long Mo? F distances of the MoF₂Mo ring are in transposition to the nitrido ligands, the bond lengths of which (165 pm) correspond to triple bonds.     

Phosphaniminato-Komplexe des Titans. Die Kristallstrukturen von [TiCl2(NPPh3)2] und [TiCl3(NPMe2Ph)(CH3CN)]2

Phosphorane Iminato Complexes of Titanium. The Crystal Structures of [TiCl₂(NPPh₃)₂] and [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ [TiCl₂(NPPh₃)₂] has been prepared by the reaction of [TiCl₃(NPPh₃)] with excess Me₃SiNPPh₃ in a melt at 220°C, forming colourless crystals. [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ is formed as yellow, moisture sensitive crystals from acetontrile solutions of [TiCl₃(NPMe₂Ph)]₂, which on its part has been obtained by the reaction of TiCl₄ with Me₃SiNPMe₂Ph. The complexes are characterized by IR spectroscopy and by crystal structure determinations. [TiCl₂(NPPh₃)₂] . Space group Fdd2, Z = 8, structure refinement with 2875 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 2080.9, b = 3308.5, c = 973.6 pm. The compound forms monomeric molecules with bond lengths TiN of 179.0 pm and PN of 156.8 pm, which correspond with double bonds. The bond angle TiNP is 166.6°. [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ . Space group P1 , Z = 1, structure refinement with 2577 unique reflections, R = 0.039 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 856.6, b = 923.1, c = 1008.3 pm, α = 81.23°, β = 71.63°, γ = 81.41°. The compound forms centrosymmetric, dimeric molecules, in which the titanium atoms are linked via chloro bridges TiCl₂Ti with TiCl bond lengths of 243.9 and 270.3 pm. In trans-position to the longer TiCl bonds the nitrogen atoms of the phosphorane iminato groups are coordinated with bond lengths TiN of 173.9 pm and PN of 161.4 pm which again correspond with double bonds. The bond angle TiNP is 156.4°.     

Reaktionen von MoNCl3 und WNCl3 mit elementarem Fluor. Kristallstrukturen von [MoO2F2(THF)2] und [WF4(NCl)(CH3CN)]

Reactions of MoNCl₃ and WNCl₃ with Elemental Fluorine. Crystal Structures of [MoO₂F₂(THF)₂] and [WF₄(NCl)(CH₃CN)] The nitrido chlorides MoNCl₃ and WNCl₃ as well as WCl₄(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF₄(NCl) and WF₄(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF₄(NCl) reacts to give [MoF₄(NCl)(THF)], which in THF solution slowly converts into [MoO₂F₂(THF)₂]. From WF₄(NCl) with acetonitrile the complex [WF₄(NCl)(CH₃CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO₂F₂(THF)₂] : Space group P2₁/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF₄(NCl)(CH₃CN)] : Space group P2₁/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º.     

Kronenetherkomplexe von Blei(II). Die Kristallstrukturen von [PbCl(18-Krone-6)][SbCl6], [Pb(18-Krone-6)(CH3CN)3][SbCl6]2, and [Pb(15-Krone-5)2][SbCl6]2

Crown Ether Complexes of Lead(II). The Crystal Structures of [PbCl(18-Krone-6)][SbCl₆], [Pb(18-Krone-6)(CH₃CN)₃][SbCl₆]₂ und [Pb(15-Krone-5)₂][SbCl₆]₂ . [PbCl(18-crown-6)][SbCl₆] has been prepared in low yield besides [Pb(CH₃)₂(18-crown-6)][SbCl₆]₂ by the reaction of Pb(CH₃)₂Cl₂ with antimony pentachloride in acetonitrile solution in the presence of 18-crown-6, forming pale-yellow crystals. The other two title compounds are formed as colourless crystals by the reaction of PbCl₂ with antimony pentachloride in acetonitrile solutions in the presence of 18-crown-6 and 15-crown-5, respectively. The complexes were characterized by IR spectroscopy and by crystal structure determinations. [PbCl(18-crown-6)][SbCl₆]: Space group P2₁/c, Z = 8, 5 003 observed unique reflections, R = 0.046. Lattice dimensions at - 80°C: a = 1 386.9; b = 1 642.7; c = 2 172.1 pm, β = 92.95°. The lead atom in the cation [PbCl(18-crown-6)]⁺ is surrounded in an almost hexagonal-planar construction by the six oxygen atoms of the crown ether and an axially oriented Cl atom. [Pb(18-crown-6)(CH₃CN)₃][SbCl₆]₂: Space group P1 , Z = 2, 6 128 observed unique reflections, R = 0.076. Lattice dimensions at - 70°C: a = 1 228.0; b = 1 422.9; c = 1 463.2 pm, α = 69.08°; β = 65.71°; γ = 64.51°. In the cation [Pb(18-crown-6)(CH₃CN)₃]²⁺ the lead atom is coordinated by the six oxygen atoms of the crown ether and by the three nitrogen atoms of the acetonitrile molecules. The structure determination is restricted by disorder. [Pb( 15-crown-5)₂][SbCI₆]₂: Space group P6₃/m, Z = 6, 5 857 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = b = 2 198.5; c = 1499.4 pm, α = β = 90°, γ = 120°. In the cation [Pb(l5-crown-5)₂]² the lead atom is sandwich-like coordinated by the ten oxygen atoms of the two crown ether molecules. The structure determination is restricted by disorder.     

Synthese und Kristallstruktur des μ-Dinitridosulfato(II)-Komplexes [Na-15-Krone-5]2[μ-(NSN)(MoF5)2]

Synthesis and Crystal Structure of the μ-Dinitridosulfate(II) Complex [Na-15-crown-5]₂[μ-(NSN)(MoF₅)₂] The title compound is formed at room temperature by the reaction of [MoCl₄(NSCl)]₂ with the equivalent amount NaF in acetonitrile in presence of the crown ether 15-crown-5. It forms black, moisture-sensitive crystals that were characterized by an X-ray structure determination (1 756 unique observed reflexions, R = 0.073). Crystal data (19°C): a = 965.5, b = 3 219, c = 1 161.1 pm, β = 95.42°; space group P2₁/n, Z = 4. The structure consists of ion triples in which the [Na-15-crown-5]⁺ ions are associated with the [μ-(NSN)(MoF₅)₂]^2? ions via Na…?F contacts of 215 to 265 pm length. Each of the two MoF₅ units of the anion is linked with one of the N atoms of the dinitridosulfate(II) group; bond angle NSN 103°, MoN bond lengths 172 pm.     

[ReCl3(NSCl)2(CH3CN)]. Synthese,IR-Spektrum und Kristallstruktur

[ReCl₃(NSCl)₂(CH₃CN)]. Synthesis, I. R. Spectrum, and Crystal Structure Black, moisture sensitive crystals of the title compound are obtained from [ReCl₃(NSCl)₂]₂ and acetonitrile in dichloromethane. The complex is characterized by its i.r. spectrum and an X-ray crystal structure determination (2483 observed independent reflexions, R = 0.035). Crystal data: triclinic, space group P1 , Z = 2, a = 681.8, b = 899.9, c = 1104.0 pm, α = 110.50, β = 97.90 and γ = 101.34°. In the monomeric [ReCl₃(NSCl)₂(CH₃CN)] molecule the Re atom has a distorted octahedral coordination with meridional arrangement of the Cl atoms. The chlorothionitrene ligands have nearly linear ReNS groups with bond lengths that correspond to double bonds (ReN 178 and 179 pm); this agrees with the NReN bond angle of 100°.     

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.     

Phosphaniminato-Komplexe von Niob und Tantal. Die Kristallstrukturen von [NbCl4(NPiPr3)(CH3CN)], [NbCl3(NPiPr3)2], [TaCl4(NPiPr3)]2 und [TaCl3(NPiPr3)2]

Phosphorane Iminato Complexes of Niobium and Tantalum. Crystal Structures of [NbCl₄(NPⁱPr₃)(CH₃CN)], [NbCl₃(NPⁱPr₃)₂], [TaCl₄(NPⁱPr₃)]₂, and [TaCl₃(NPⁱPr₃)₂] The title compounds have been prepared from the pentachlorides of niobium and tantalum with the silylated phosphorane imine Me₃SiNPⁱPr₃. They are characterized by IR spectroscopy and crystal structure determinations. NbCl₄(NPⁱPr₃)(CH₃CN)] . Space group Pna2₁, Z = 4, 2102 observed unique reflections, R = 0.022. Lattice dimensions at ?50°C: a = 1627.2, b = 876.3, c = 1335.3 pm. The compound forms monomeric molecules with the acetonitrile molecule in trans position to the phosphorane iminato group. This group shows a short NbN distance of 178.2 pm with a NbNP bond angle of 165.2°. [NbCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 2534 observed unique reflections, R = 0.046. Lattice dimensions at 20°C: a = 1302.65, b = 1321.69, c = 1672.04 pm, β = 111.713°. The compound forms monomeric molecules with a distorted bipyramidal surrounding of the niobium atom and equatorially arranged phosphorane iminato groups. [TaCl₄(NPⁱPr₃)]₂ . Space group Pbca, Z = 4, 1537 observed unique reflections, R = 0.037. Lattice dimensions at ?40°C: a = 1420.6, b = 1483.9, c = 1622.0 pm. The compound forms centrosymmetric dimeric molecules with dissimilarly long Ta₂Cl₂ bridges and equatorially arranged phosphorane iminato groups. [TaCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 5737 observed unique reflections, R = 0.039. Lattice dimensions at ?50°C: a = 1303.9, b = 1327.2, c = 1682.1 pm, β = 111,92°. The compound is isotypical with the corresponding niobium compound.     

Synthese,Schwingungsspektren und Kristallstrukturen der Nitratoargentate (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN und (Ph4P)[Ag2(NO3)3]

Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN and (Ph₄P)[Ag₂(NO₃)₃] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN ( 1 ), whereas (Ph₄P)[Ag₂(NO₃)₃] ( 2 ) is obtained in a long‐time reaction from (Ph₄P)Br and excess AgNO₃ in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R₁ = 0.0348. 1 contains isolated complex units [Ag(NO₃)₂(CH₃CN)]^?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH₃CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R₁ = 0.072. In the polymeric anions [Ag₂(NO₃)₃]^? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph₄P)⁺ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms.     

PPh3Me[MoBr5(CH3CN)]. IR-Spektrum,magnetisches Verhalten und Kristallstruktur

PPh₃Me[MoBr₅(CH₃CN)]. I.R. Spectrum, Magnetic Behaviour, and Crystal Structure Molybdenum tetrabromide and acetonitrile form MoBr₄(CH₃CN)₂, from which PPh₃Me[MoBr₅(CH₃CN)] is obtained by reaction with PPh₃MeBr in dibromo methane. Both compounds are characterized by their IR spectra. By evaluation of the magnetic susceptibility of PPh₃Me[MoBr₅(CH₃CN)] in the temperature range of 4.2 to 290 K the Curie-Weiss parameters μ_cw = 2.65 B.M. and Θ = ?44 K were obtained. The crystal structure of PPh₃Me[MoBr₅(CH₃CN)] was determined by X-ray diffraction (2426 observed reflexions, R = 0.082). Crystal data: a = 1064.9, b = 2172.1, c = 1330.4 pm, β = 119.92º, space group P2₁/c, Z = 4. In the crystal, PPh₃Me⁺ and [MoBr₅(CH₃CN)]^? ions are packed in alternate cation and anion layers perpendicular to a. In the anion the Mo atom has a distorted octahedral coordination. The bond length of the bromine atom in trans position to the N atom is considerably shorter than the other MoBr distances.     

[Sb(12-Krone-4)2(CH3CN)][SbCl6]3 und [Bi(12-Krone-4)2(CH3CN)][SbCl6]3, die ersten Trikationen von Antimon(III) und Bismut(III)

[Sb(12-Crown-4)₂(CH₃CN)][SbCl₆]₃ and [Bi(12-Crown-4)₂(CH₃CN)][SbCl₆]₃, first Trications of Antimony(III) and Bismuth(III) The crown ether complexes [M(12-crown-4)₂(CH₃CN)][SbCl₆]₃ with M = Sb and Bi are formed by the reaction of antimony trichloride and bismuth trichloride, respectively, with antimony pentachloride in acetonitrile solution in the presence of 12-crown-4. They form colourless, moisture sensitive crystals, which were characterized by X-ray structure determinations and by IR spectroscopy. The complex with M = Sb was also characterized by ¹²¹Sb Mössbauer spectroscopy. Both complexes crystallize isotypically in the orthorhombic space group Pbcn with four formula units per unit cell. M = Sb: 3 483 observed unique reflections, R = 0.038. M = Bi: 2 958 observed unique reflections, R = 0.036. The compounds consist of SbCl₆^? ions and trications [M(12-crown-4)₂(CH₃CN)]³⁺, in which the M³⁺ ions are ninefold coordinated by the eight oxygen atoms of the crown ether molecules and by the nitrogen atom of the acetonitrile molecule. The lone pair of the M³⁺ ions has no steric effect.     

Synthese,Kristallstrukturen und 121Sb-Mößbauer-Spektren von [SbBr3(15-Krone-5)], [SbBr2Me(15-Krone-5)] und [SbBr2Ph(15-Krone-5)]

Synthesis, Crystal Structure, and ¹²¹Sb-Mössbauer Spectra of [SbBr₃(15-Crown-5)], [SbBr₂Me(15-Crown-5)], and [SbBr₂Ph(15-Crown-5)] The compounds [SbBr₃(15-crown-5)] ( 1 ), [SbBr₂Me(15-crown-5)] ( 2 ), [SbBr₂Ph(15-crown-5)] ( 3 ), and [SbCl₂Me(15-crown-5)] ( 4 ) are formed by the reaction of 15-crown-5 with SbBr₃, SbBr₂Me, SbBr₂Ph, and SbCl₂Me, respectively, in toluene solution at ?40°C. The complexes were characterized by IR spectroscopy, ¹²¹Sb-Mössbauer spectroscopy, 1–3 as well as by X-ray structure determinations.

• 1 : Space group P2₁2₁2₁, Z = 4, 1735 observed, independent reflections, R = 0.050, Lattice dimensions at ?65°C: a = 787.03(7); b = 1313.0(2); c = 1619.3(2) pm.
• 2 : Space group Pca2₁, Z = 8, 2730 observed, independent reflections, R = 0.050, Lattice dimensions at ?65°C: a = 1308.2(2); b = 1611.8(2); c = 1640.5(3) pm.
• 3 : Space group P2₁/n, Z = 4,2458 observed, independent reflections, R = 0.040, Lattice dimensions at ?60°C: a = 900.3(3); b = 1390.6(6); c = 1618.5(7) pm, β = 96.32(3)°.

The complexes 1–3 have molecular structures, in which the antimony atoms are surrounded by the five oxygen atoms of the crown ether molecule and by three ligands Br₃, Br₂CH₃, Br₂Ph, respectively.     

Die Kristallstruktur von [TeCl3(15-Krone-5)]SbCl6

The Crystal Structure of [TeCl₃(15-crown-5)]SbCl₆ The title compound is synthesized by the reaction of tellur tetrachloride, 15-crown-5 and antimony pentachloride in acetonitrile solution, forming colourless crystals, which were characterized by IR spectroscopy and an X-ray structure determination. Space group Pnma, Z = 4, 1966 observed unique reflections, R = 0.072, R_w = 0.052. The compound forms ions [TeCl₃(15-crown-5)]⁺ and SbCl₆^?; in the cation the tellurium atom is eightfold coordinated by the three chlorine atoms and the five oxygen atoms of the crownether molecule (Te? O bond lengths 266 and 279 pm).     

Synthese und Kristallstruktur des tetrameren Nitridokomplexes [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2]

Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH₃CN)₄]₂[W₄N₄Cl₁₄(CH₃CN)₂] . The title compound has been prepared by the reaction of CuCl with WNCl₃ in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH₃CN)₄]⁺ ions, which are arranged to form strands, and of anions [W₄N₄Cl₁₄(CH₃CN)₂]^2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.     

[Li(THF)][Zn3(CH2CN)3(LiBr)(NPMe3)4] — ein funktionalisierter Phosphaniminato‐Komplex von Zink mit supramolekularer Struktur

[Li(THF)][Zn₃(CH₂CN)₃(LiBr)(NPMe₃)₄] — a functionalized Phosphoraneiminato Complex of Zinc with Supramolecular Structure [Li(THF)][Zn₃(CH₂CN)₃(LiBr)(NPMe₃)₄] ( 1 ) has been prepared from the heterocubane [ZnBr(NPMe₃)]₄ and LiCH₂CN in tetrahydrofuran suspension to give colourless crystals which were characterized by IR‐spectroscopy and by a crystal structure analysis. 1 crystallizes in the orthorhombic space group Pnam with four units per unit cell. Lattice dimensions at 203 K: a = 2156.9(10), b = 1546.9(14), c = 1226.2(4) pm, R₁ = 0.0756. The structure consists of the anionic heterocubane [Zn₃(CH₂CN)₃(LiBr)(NPMe₃)₄]^—, the eight skeleton atoms of which are the three zinc atoms and the lithium atom as well as the four nitrogen atoms of the phosphoraneiminato groups. The charge of this anionic cube is compensated by a Li⁺‐ion to which is coordinated a THF molecule, as well as three cyanomethyl‐nitrogen atoms of three different cubes. This results in the formation of a three‐dimensional supramolecular structure.     

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.     

[{Y(OH)(Benzo-15-Krone-5)(CH3CN)}2]I4, ein Salz mit einem dimeren,hydroxidverbrückten out-of-cavity-Komplex

[{Y(OH)(Benzo-15-Crown-5)(CH₃CN)}₂]I₄, a Salt with a Dimeric Hydroxide-Bridged out-of-cavity Complex Coulorless single crystals of [{Y(OH)(Benzo-15-Crown-5)(CH₃CN)}₂]I₄ are obtained from the reaction of YI₃ and benzo-15-crown-5 in acetonitrile. The crystal structure (monoclinic, P2₁/c, Z = 2, a = 1198.1(1), b = 1375.9(2), c = 1623.5(2) pm, β = 106.50(1)° R1 = 0.0843, wR2 = 0.2193 contains the hydroxide-bridged cationic out-of-cavity dimer.     

Synthese von Nitrenkomplexen mit N-Trimethylsilylanilin. II. Charakterisierung und Kristallstruktur der Rhenium(V)-phenylnitren-Komplexe mer-[Re(NPh)Cl3(NH2Ph)(Ph3P)] und trans-[Re(NPh)(OMe)Cl2(Ph3P)2]

Synthesis of Phenylnitrene Complexes with N-Trimethylsilylaniline. II. Characterization and Crystal Structure of the Rhenium(V) Complexes mer-[Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] and trans-[Re(NPh)(OMe)Cl₂(Ph₃P)₂] Reaction of [ReOCl₃(Ph₃P)₂] with N-trimethylsilylaniline yields mer-[Re(NPh)Cl₃(Ph₃P)₂], which reacts under air with excess of N-trimethylsilylaniline to form [Re(NPh)Cl₃ · (NH₂Ph)(Ph₃P)]. Crystallization from CH₂Cl₂/MeOH affords [Re(NPh)(OMe)Cl₂(Ph₃P)₂] as an additional product. [Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] crystallizes in the monoclinic space group P2₁/n with a = 1 192.3(3); b = 1 918.9(3); c = 1 266.3(3) pm; β = 101.71(1)°; Z = 4. The rhenium atom has a distorted octahedral environment with the Cl atoms in meridional positions. The phenyl nitrene ligand is coordinated with an almost linear arrangement Re? N1? C40 = 166.8(6)° and with a bond distance Re?N = 170.5(6) pm. [Re(NPh)(OMe)Cl₂(Ph₃P)₂] · 1/2CH₂Cl₂ crystallizes in the triclinic space group P1 : a = 1 103.1(4); b = 1 227.9(4); c = 1 711.3(5) pm; α = 70.48(3)°; β = 72.71(3)°; γ = 80.03(3)°; Z = 2. The rhenium atom exhibits a distorted octahedral coordination with the Cl atoms and the phosphine ligands in trans positions. As a consequence of the competition of the nitrene ligand and the trans-coordinated methoxy group the Re?;N bond length is slightly lengthened to 173.2(7) pm, while the Re? O bond length of 193.4(6) pm is short. The bond angles Re? N? C70 and Re? O? C80 are 173.3(7)° and 139.1(7)°, respectively.