Synthesen und Kristallstrukturanalysen von [SbI3(SbMe3)(THF)]2 und [Li(THF)4]2[Bi2Cl8(THF)2]

Syntheses and Crystal Structure Analyses of [SbI₃(SbMe₃)(THF)]₂ and [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] The reaction of Me₃Sb with SbI₃ in tetrahydrofuran (THF) gives [SbI₃(SbMe₃)(THF)]₂ ( 1 ). [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] ( 2 ) is formed by reaction of LiCl and BiCl₃ in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.     

Synthese und Kristallstruktur von Tetraphenylphosphonium-Aquabis(tetrasulfido)thionitrosyl-Osmat,PPh4[Os(NS)(S4)2(H2O)]

Synthesis and Crystal Structure of Tetraphenylphosphonium Aqua-bis(tetrasulfido)thionitrosyl Osmate, PPh₄[Os(NS)(S₄)₂(H₂O)] PPh₄[Os(NS)(S₄)₂(H₂O)] has been prepared as redbrown crystals by reacting PPh₄[OsNCl₄] with a solution of excess disodium tetrasulfide in dimethylformamide/H₂O and characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/n, Z = 4, structure solution with 4162 independent reflections, R = 0.059 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 1138.9(5), b = 1301.4(4), c = 2092.7(7) pm, β = 104.74(3)º. Os? N, Os? O, and Os? S distances are 175.2(12), 219.8(12), and 237.5(4)?239.1(4) pm, respectively. The Os?N?S moiety is approximately linear, with an OsNS angle of 171.2(7)º.     

Synthese und Kristallstruktur von [Na(12-Krone-4)2]2[Hg(Se4)2] · 1,5 DMF

Synthesis and Crystal Structure of [Na(12-Crown-4)₂]₂[Hg(Se₄)₂] · 1.5 DMF . The title compound has been prepared by the reaction of Na₂Se₄ with mercury acetate in DMF solution in the presence of 15-crown-5, forming dark red crystal needles. [Na(12-crown-4)₂]₂[Hg(Se₄)₂] · 1.5 DMF crystallizes in the space group C2/c with eight formula units per unit cell. The structure was determined with 3 824 observed unique reflections, R = 0.085. Lattice dimensions at - 70°C: a = 2 884(2), b = 1 407.7(7), c = 2 843(2) pm, β = 93.93(5)°. The structure consists of [Na(12-crown-4)₂]⁺ ions with a sandwichlike coordination of the crown ether molecules, and of [Hg(Se₄)₂]^2? ions, in which the mercury atom is coordinated by two tetraselenido ions in a chelating fashion. The [Hg(Se₄)₂]^2? ions are arranged to infinite chains via Se…?Se contacts.     

Die Kristallstruktur von K[F5W(≡NCl)]

Crystal Structure of K[F₅W(≡NCl)] Orange single crystals of K[F₅W(≡NCl)] have been formed as a by‐product from the reaction of tungsten nitrido chloride, WNCl₃, with Me₃SnF in the presence of potassium fluoride in toluene suspension. K[F₅W(≡NCl)] crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. Lattice dimensions at –83 °C: a = 1145.9(3), b = 770.4(2), c = 772.5(2) pm, β = 99.91(1)°, R₁ = 0.0742. The compound forms an ionic structure with octahedral [F₅W(≡NCl)]^– ions with a nearly linear arrangement of the N‐chloroimido ligand group W≡N–Cl (bond angle 173°, WN distance 174 pm). The K⁺ ions link the anions via K…F contacts and coordination number eight to form double layers along [100]. The layers itself are associated by short bounding Cl…F contacts of 279 pm.     

Kristallstruktur von (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2

Crystal Structure of (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ . (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ crystallizes from hydrobromic acid solution of Re₃Br₉ · 2 H₂O and NMe₄Br at 0 – 5°C. The crystal structure (monoclinic; P2₁/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; R_w = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re₃Br₁₁(H₂O)]^2? units and neutral cluster units that are connected through crystal water molecules to chains{[Re₃Br₉(H₂O)₃](H₂O)₂}.     

Synthese und Kristallstruktur von [(n‐Bu)4N][W6Cl18]

Synthesis and Crystal Structure of [(n‐Bu)₄N][W₆Cl₁₈] Single‐crystals of [(n‐Bu)₄N][W₆Cl₁₈] were obtained as thin needles by adding methanol to a solution of W₆Cl₁₈ and [(n‐Bu)₄N]Cl in tetrahydrofuran. The structure was determined by single‐crystal X‐ray diffraction at 210 K. [(n‐Bu)₄N][W₆Cl₁₈] crystallizes in the monoclinic space group C 2/c with Z = 8 and the lattice parameters a = 2175.6(1) pm, b = 1738.0(1) pm, c = 2160.36(9) pm, and β = 91.680(5) °. The crystal structure contains isolated [(W₆Cl₁₂ⁱ)Cl₆^a]^— clusters and [(n‐Bu)₄N]⁺ ions.     

Kristallstruktur von [ZnH(NPMe3)]4, einem tetrameren Phosphaniminato-Komplex des Zinks mit terminalen Hydrido-Liganden

Crystal Structure of [ZnH(NPMe₃)]₄, a Tetrameric Phosphoraneiminato Complex of Zinc with Terminal Hydrido Ligands The crystal structure of the title compound, which crystallizes as [ZnH(NPMe₃)]₄ · 4 THF forming colourless, very reactive blocks, obtained by recrystallization from toluene, reveals discrete tetrameric molecules with heterocubane structure with almost undistorted Zn₄N₄ cubic skeletons. The hydrido ligands assume terminal exocyclic positions with Zn–H bond lengths of 150 pm in average.     

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.     

Kristallstruktur des Lithium‐Trimethylsilanolats [Li7(OSiMe3)7(THF)]

The lithium silanolate LiOSiMe₃ is accessible from the reaction of Me₃SiOSiMe₃ with LiMe in tetrahydrofuran. Single crystals of [Li₇(OSiMe₃)₇(THF)] were obtained from toluene at 25 °C. The structure of [Li₇(OSiMe₃)₇(THF)] (C2/c) features a capped trigonal antiprismatic arrangement of seven Li atoms. The Li atoms in [Li₇(OSiMe₃)₇(THF)] are μ₃‐bridged by seven O atoms of the silanolate ligand.     

[W(NPPh3)4]Cl2 — Ein Phosphaniminato-Komplex mit einem Wolfram-Dikation

[W(NPPh₃)₄]Cl₂ — a Phosphoraneiminato Complex with a Dication of Tungsten The title compound has been prepared by the reaction of Me₃SiNPPh₃ with WNCl₃ and WO₂Cl₂, respectively, in acetonitrile, forming colourless crystals, which were characterized by IR spectroscopy and by an X-ray structure determination. Space group P2₁/n, Z = 4, 4 424 observed unique reflections, R = 0.045. Lattice dimensions at 20°C: a = 1 206.5(2), b = 2 225.3(2), c = 2 421.0(3) pm, β = 101.09(1)°. In the dication [W(NPPh₃)₄]²⁺ the tungsten atom is surrounded in a tetrahedral fashion by the four nitrogen atoms of the phosphoraneiminato ligands. The bond lengths WN and PN correspond with double bonds.     

Synthese und Kristallstruktur von [Na(15-Krone-5)]4[Cd4Te12] · 8 DMF

Synthesis and Crystal Structure of [Na(15-Crown-5)]₄[Cd₄Te₁₂] · 8 DMF The title compound has been prepared by reaction of Na₂Te₃ with cadmium acetate in DMF solution in the presence of 15-crown-5, forming black crystal needles, which were characterized by an X-ray structure determination. Space group P2₁/n, Z = 2, 5 716 observed unique reflections, R = 0.038. Lattice dimensions at ?50°C: a = 1 622.9, b = 2 038.2, c = 1 739.8 pm, β = 92.26°. The compound has an ionic structure. The cations [Na(15-crown-5)(DMF)]⁺ and [Na(15-crown-5) · (DMF)₂]⁺ together with two further DMF molecules form tetrameric units. In the centrosymmetric anions [Cd₄Te₁₂]^4? the cadmium atoms are linked by μ₂-Te^2?-, μ₄-Te₂^2?-, and μ₂-Te₃^2?-units.     

Darstellung und Kristallstruktur von K4[SnO3]

Preparation and Crystal Structure of K₄[SnO₃] K₄[SnO₃] crystallizes with the K₄[PbO₃] structure in the orthorhombic spacegroup Pbca (No. 61) with the lattice constants a = 652.2(3) pm, b = 1 112.1(5) pm and c = 1 893.7(7) pm. In the structure isolated ψ-tetrahedral anions [Sn^IIO₃]^4? are arranged in layers perpendicular [001]. The structure of K₄[SnO₃] will be compared with those of stannates and plumbates of composition A₄[M^IIO₃] (A = Na, K, Rb, Cs) and with the known potassium stannates(II).     

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.     

Hydrogendiazid Synthese und Kristallstruktur von PPh4[N3HN3]

Hydrogen Diazide – Synthesis and Crystal Structure of PPh₄[N₃HN₃] PPh₄[N₃HN₃] has been prepared from PPh₄N₃ and Me₃SiN₃ by the reaction with water or ethanol forming colourless nonexplosive crystal needles, which were characterized by IR spectroscopy and by a crystal structure determination. Space group C2/c, Z = 12, lattice dimensions at –70 °C: a = 3782.4(3), b = 727.8(2), c = 2512.4(2) pm, β = 110.13(1)°, R = 0.0841. The [N₃HN₃]^– ion is characterized by an asymmetric N–H…N hydrogen bridge with a NN distance of 272(1) pm.     

Kristallstrukturen von [TiF3(NPPh3)(HNPPh3)]2 und von HNPPh3

Crystal Structures of [TiF₃(NPPh₃)(HNPPh₃)]₂ and of HNPPh₃ The phosphoraneiminato-phosphaneimine complex [TiF₃(NPPh₃)(HNPPh₃)]₂ was obtained by the reaction of TiF₄ with Me₃SiNPPh₃ in boiling dichloromethane. It crystallizes from 1,2-dichloroethane as yellow crystals which include four molecules C₂H₄Cl₂ per dimeric formula unit. Space group P2₁/n, Z = 2, structure solution with 7270 independent reflections, R = 0.060 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1417.5, b = 1896.9, c = 1586.6 pm, β = 101.22°. The compound forms centrosymmetric dimeric molecules via μ₂-F bridges with TiF distances of 194.6 and 223.3 pm, the longer one being in trans-position to the N atom of the (NPPh₃)^? ligand. Its TiN bond length of 177.7 pm corresponds with a double bond. The TiN bond length of the HNPPh₃ donor molecule of 213.4 pm is typical for a donor acceptor bond. According to the crystal structure determination the phosphaneimine HNPPh₃ forms monomeric molecules without intermolecular hydrogen bridges with a PN bond length of 152.4 pm. Space group P2₁/c, Z = 4, structure solution with 3229 independent reflections, R = 0.062 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1460.4, b = 928.9, c = 1096.6 pm, β = 93.35°.     

Kristallstruktur,Schwingungsspektren und Normalkoordinatenanalyse von K2[IrCl5(NH3)]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of K₂[IrCl₅(NH₃)] The X-ray structure determination of K₂[IrCl₅(NH₃)] (orthorhombic, space group Pnma, a = 13.426(4), b = 10.015(2), c = 6.8717(7) Å, Z = 4) revealed the C_s point symmetry of the complex anion [IrCl₅(NH₃)]^2? (Ir? Cl = 2.337–2.365, Ir? N = 2.067(10); N? H = 0.73–0.79 Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(NH) = 5.88, f_d(IrN) = 2.66, f_d(IrCl) = 1.68 mdyn/Å.     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

Eine neue und unerwartete Form des Dodecaiodid-Ions I122–: Darstellung und Kristallstruktur des Bis[kalium(dibenzo-18-krone-6)]dodecaiodids [K(C20H24O6)]2I12

Studies of Polyhalides. 32. A New and Unforeseen Shape of the Dodecaiodide Ion I₁₂^2–: Preparation and Crystal Structure of Bis[potassium(dibenzo-18-crown-6)]dodecaiodide [K(C₂₀H₂₄O₆)]₂I₁₂ Particularly iodine rich polyiodides tend to form extended iodine nets by multiply concatenating iodide or triiodide ions through iodine molecules. Therefore the discovery of a not ramified, nearly isolated dodecaiodide ion I₁₂^2– in the new compound [K(C₂₀H₂₄O₆)]₂I₁₂ seems to be unexpected. This ion may be described as an extraordinary long fragment of the triiodide-iodine chain (I₃^– · I₂)_∞.     

Synthese und Kristallstrukturen der Nitridodiolato-Osmate(VI) PPh4[OsNCl2(O2C2H4)] und PPh4[OsNCl2(O2C2Me4)] · 2 THF

Syntheses and Crystal Structures of the Nitridodiolato Osmates(VI) PPh₄[OsNCl₂(O₂C₂H₄)] and PPh₄[OsNCl₂(O₂C₂Me₄)] · 2 THF The title compounds were prepared by the reaction of PPh₄[OsNCl₄] with glycole and pinacole, respectively, in CH₂Cl₂ and THF, respectively, in the presence of triethylamine, forming orange-red single crystals. According to the crystal structure determinations the compounds have ionic structures. In the anions the nitrido ligand occupies the apical position of the distorted tetragonal pyramid, and the two chlorine atoms and the two oxygen atoms of the diolato ligands are in equatorial positions. PPh₄[OsNCl₂(O₂C₂H₄)] : Space group P2₁/n, Z = 4, 3 331 observed unique reflections, R = 0.031. Lattice dimensions at 19°C: a = 1 750.3, b = 816.8, c = 1 816.5 pm, β = 95.16°. PPh₄[OsNCl₂(O₂C₂Me₄)] · 2 THF : Space group P1 , Z = 2, 5 238 observed unique reflections, R = 0.051. Lattice dimensions at -80°C: a = 898.9, b = 1 405.1, c = 1 518.6 pm, α = 93.66°, β = 92.89°, γ = 92.51°.