Reaktionen von Diorganogallium(indium)fluoriden. Die Kristallstruktur von Mes2InF

Reaction of Diorganogallium(indium) Fluorides. The Crystal Structure of Mes₂InF Mes₂GaF ( 1 ) reacts with t-BuNH₂ at 20°C to the amine adduct [Mes₂Ga(F)(t-BuNH₂)] ( 2 ). Treatment of 1 with H₂S gives after a redox reaction γ-S₈-Sulfur (Muthmanns' Sulfur) ( 3 ) as the only isolated product. When i-Pr₂InF ( 4 ) is reacted with [SnCl₂(dioxane)] in toluene at 70°C one yields after workup [i-PrInCl₂(dioxane)] ( 5 ), which is formed after ligand exchange and reaction with dioxane. 2 and 5 were investigated by NMR-, IR- and MS-techniques. In addition, 2 · 2,5 THF, 3, 5 and Mes₂InF were characterized by an X-ray structure determination. According to that 2 · 2,5 THF contains dimeres, associated by hydrogen brigdes, while 5 possesses a polymeric structure with bridging dioxane molecules. 3 forms eightmembered rings with C ₂-symmetry. Me₂InF is a trimer in the solid state with an In₃F₃-backbone.     

Darstellung und Charakterisierung von Organodilithiumphosphiden. Die Kristallstruktur von [Li(THF)(TMEDA)P(H)Mes]

Synthesis and Characterization of Organodilithium Phosphides. The Crystal Structure of [Li(THF)(TMEDA)P(H)Mes] t-BuPH₂ and MesPH₂ can be reacted with two equivalents n-BuLi at R. T. in Et₂O/n-hexane to yield the corresponding organodilithium phosphides t-BuPLi₂ ( 1 ) and MesPLi₂ ( 2 ). 1 and 2 can be isolated solvent-free as bright orange-yellow solids. 1 and 2 were characterized by NMR, IR, and RE spectra. When MesPH₂ is treated with one equivalent of n-BuLi, MesP(H)Li is crystallizing as [Li(THF)(TMEDA)P(H)Mes] ( 3 ) from THF/TMEDA/n-pentane in the space group P2₁/n with a = 893.41(6), b = 1 734.7(1), c = 1 391.1(1) pm and β = 90.613(6)°.     

Die Kristallstruktur von AgIIF[AgIIIF4]

Crystal structure of Ag^IIF[Ag^IIIF4] For the first time dark brown single crystals of mixedvalent AgF[AgF₄] were isolated under solvothermal conditions out of anhydrous HF/F₂. The compound crystallizes in a new type of structure, triclinic with a = 499.9(2) pm, b = 1108.7(5) pm, c = 735.7(3) pm, α = 90.05(3)°, β = 106.54(4)°, γ = 90.18(4)°, spcgr. P1¯ — C_i¹ (No. 2) and Z = 4.     

Mesityltrifluorogallate. Die Kristallstrukturen von Cs[MesGaF3] und K[MesInBr3]

Mesityltrifluoro Gallates. The Crystal Structures of Cs[MesGaF₃] and K[MesInBr₃] Mes₃Ga reacts with GaBr₃ in the ratio 1:2 in a commutation reaction to MesGaBr₂ ( 1 ). 1 can be reacted with KF and CsF in MeCN to K[MesGaF₃] ( 2 ) and Cs[MesGaF₃] ( 3 ), respectively. K[MesInBr₃] ( 4 ) was isolated when MesInBr₂ was treated with KF in MeCN. The use of 15-crown-5 was leading to [K(15-crown-5)₂][Mes₂InBr₂] ( 5 ) in a substituent exchange reaction. 1-5 were characterized by NMR-, IR- and MS-techniques. The solid state structures of 3 and 4 could be established by X-ray structure determinations. According to these determinations, a layer-type arrangement of the molecules is both structures in common. In the center of the layers, ionic interactions were formed, while the separation of the layers is caused by the bulky mesityl substituents.     

Synthese und Kristallstruktur von [Cr(NH3)6][Cr(NH3)2F4][BF4]2

Synthesis and Crystal Structure of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂ The action of ammonium fluoride on a mixture of boron and chromium in a sealed Monel ampoule at 300 °C yields single crystals of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂. The crystal structure (tetragonal, P4/mbm, Z = 2, a = 1056.0(1), c = 781.7(1) pm; R₁ = 0.0414; wR₂ = 0.1087 for 411 reflections with I₀ > 2σ(I)) contains [Cr(NH₃)₆]³⁺ and [Cr(NH₃)₂F₄]^– octahedra and twice as many [BF₄]^– tetrahedra that are arranged in a quadrupled super‐structure of the CsCl‐type of structure.     

Synthese und Kristallstruktur von [Fe(MeCN)6][Fe2OCl6]

Synthesis and Crystal Structure of [Fe(MeCN)₆][Fe₂OCl₆] [Fe(MeCN)₆][Fe₂OCl₆] ( 2 ) is obtained by passing dry air through a solution of FeCl₂ in acetonitrile in almost quantitative yield. 2 crystallises in the trigonal space group R 3 [a = b = 12.121(1), c = 29.875(6) Å, Z = 6]. The oxygen atom in the Fe₂OCl₆ anion occupies the 3 position and causes therefore an Fe–O–Fe angle of 180°. The refinement in the triclinic space group P1 leads to a slightly bent arrangement of the Fe–O–Fe fragment.     

Die Kristallstruktur von [Cl3PNPCl3][VOCl4]

Investigations on Electronically Conducting Oxide Systems. XIV. Solid Solutions and Conductivity in the System MgTiO₃? Ti₂O₃ Solid solution formation and conductivity is reported for the system Mg_1?xTiTiO₃ (0 < x < 1). Ti^III atoms are predominantly substituted in pairs for Mg^II and Ti^IV. In the range of low x values Ti^III? Ti^III bonds typical for Ti₂O₃ in the semiconducting state are very weakened because of the distances preserved in the host lattice of MgTiO₃. Up to x = 0,5 EPR measurements at 77 K indicate magnetic “dimers” with S = 1 at a distance of 550 pm resulting from antiparallel spin orientation of the Ti^III pairs and transfer of the magnetic interaction by super exchange to a next-neighboured Ti^III pair. Electrical conductivity is caused by polaron hopping. The steep increase in the range of small Ti^III concentration is interpreted by a screening field approximation.     

Synthese und Strukturuntersuchungen von Iodocupraten(I). XV Iodocuprate(I) mit solvatisierten Kationen: [Li(CH3CN)4][Cu2I3] und [Mg{(CH3)2CO}6][Cu2I4]

Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH₃CN)₄] [Cu₂I₃] and [Mg{(CH₃)₂CO}₆][Cu₂I₄] [Li(CH₃CN)₄][Cu₂I₃] 1 and [Mg((CH₃)₂CO)₆][Cu₂I₄] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI₂ in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH₃CN)₄]⁺ cations are located between rod packings of CuI₄ tetrahedra double chains [(CuI_2/2I_2/4)₂]^? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P2₁/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH₃)₂CO)₆]²⁺ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu₂I₄]^2? occupy holes in the trigonal prismatic channels formed by the cations.     

Synthese und Kristallstruktur von [Ba(18-Krone-6)(DMF)4][Cd(Se4)2]

Synthesis and Crystal Structure of [Ba(18-Crown-6)(DMF)₄][Cd(Se₄)₂] The title compound has been prepared by the reaction of a DMF-solution of lithium polyselenide with BaSe₂ and cadmium acetate in the presence of 18-crown-6, forming black crystals. The compound was characterized by IR spectroscopy and by an X-ray structure determination. Space group P2/a, Z = 4, 5392 observed unique reflections, R = 0.048. Lattice dimensions at ?90°C: a = 2021.9(12); b = 1019.8(6); c= 2270.8(14)pm, ß = 106.98(4)°. The structure consists of [Ba(18-crown-6)(DMF)₄]²⁺ ions, in which the barium ions are coordinated by the six oxygen atoms of the crown ether molecule and by four oxygen atoms of the DMF molecules, and of [Cd(Se₄)₂]^2? ions. The cadmium atoms are coordinated by two tetraselenide ions in a chelating fashion.     

Die Kristallstruktur von Lithiummetaperiodat,LiIO4

The Crystal Structure of Lithiummetaperiodate, LiIO₄ For the first time single crystals of LiIO₄ were obtained. According to the results of an X-ray structure determination (monoclinic, P2₁/n; a = 525.5(3), b = 851.1(4), c = 796.9(5) pm, β = 104.21(3)°; Z = 4; 2 148 diffractometer data, R = 0.024) the coordination by oxygen is tetrahedral for iodine and strongly distorted trigonal bipyramidal for lithium. Two lithium-oxygen-polyhedra are connected via a common edge. LiIO₄ crystallises isostructural to LiAlH₄. The structure is discussed and compared to those of other metaperiodates and tetrahydridoaluminates.     

Die Kristallstruktur von CsTcO4 [1]

The Crystal Structure of CsTcO₄ CsTcO₄ crystallizes orthorhombic with a = 5.72₇, b = 5.92₁ and c = 14.34 Å. Z = 4, space group Pnma (Nr. 62, I.T.). The metal positions were refined by single crystal data, the oxygen positions first determined: the CsTcO₄ structure is a slight distortion of the scheelite arrangement (parameters: see text). The MADELUNG Part of Lattice Energy, MAPLE, ?Mean Effective Ionic Radii”?, MEIR, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Die Kristallstruktur von Na4CoO4[1]

The Crystal Structure of Na₄CoO₄ According to X-Ray investigations on single crystals, Na₄CoO₄ crystallizes triclinic (P1, a = 8.64₈, b = 5.70₂, c = 6.40₀ Å, α = 123.9°, β = 98.1°, γ = 99.2°). There are almost tetrahedral CoO₄-groups; sodium is coordinated by four or five O^2?.     

Low‐Temperature Isolation of the Bicyclic Phosphinophosphonium Salt [Mes*2P4Cl][GaCl4]

The reaction of [ClP(μ‐PMes*)]₂ ( 1 ) with the Lewis acid GaCl₃ yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan‐2‐ium salt, [Mes*P₄(Cl)Mes*][GaCl₄] ( 3 [GaCl₄]), which incorporates a positively charged phosphonium center within its bicyclic P₄ scaffold. The formation of the title compound was studied by means of low‐temperature NMR experiments. This led to the identification of an intermediate cyclotetraphosphenium cation, which was trapped by reaction with dimethylbutadiene (dmb). All of the compounds were fully characterized by experimental and computational methods.     

Mesityloxomolybdän- und -wolfram-Verbindungen. I. Die Struktur von LiMoO2Me2Mes(OEt2)2

Mesityl Oxo Molybdenum and Tungsten Compounds. I. Structure of LiMoO₂Me₂Mes(OEt₂)₂ LiMoO₂Me₂Mes(OEt₂)₂ 2 is prepared by literature method [2] from MoO₂Mes₂ 1 and LiMe. Its x-ray structure and NMR-spectral data are presented. 2 adopts a dimer structure in which two [MoO₂Me₂Mes]^? anions are linked via two bridging [Li(OEt₂)₂]⁺ cations bonded to the oxo ligands. The resulting [‥OMoOLi‥]₂ ring is planar.     

Darstellung und Kristallstruktur von (CH3NH3)8[NdCl6][NdCl4(H2O)2]2Cl3

Preparation and Crystal Structure of (CH₃NH₃)₈[NdCl₆][NdCl₄(H₂0)₂]₂Cl₃ (CH₃NH₃)₈[NdCl₆][NdCl₄ (H₂O)₂]₂Cl₃ is for the first time prepared and investigated by X-ray, single crystal work. It crystallizes in the monoclinic system (space group C2/m, Z = 2) with a = 9.358(5), b = 17.424(9), c = 15.360(8) Å, β = 108.30(4)°. The structure contains besides isolated Cl^? ions distorted [NdCl₆]^3? octahedra and [NdCl₄(H₂O)₂]^? chains.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

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.     

Darstellung und Kristallstruktur von [Li(DME)2I]

Synthesis and Crystal Structure of [Li(DME)₂I] . LiI can be dissolved at 50°C in toluene/DME (2:1). At - 20°C [Li(DME)₂I] ( 1 ) was isolated in 75% yield. 1 was characterized by NMR techniques as well as an X-Ray structure determination. 1 crystallizes in the space group C2/c with a = 1 356.9(2), b = 813.2(1), c = 1 259.1(2) pm, and β = 99.74(1)°.     

Zur Kristallstruktur von Ca2PbO4

On the Crystal Structure of Ca₂PbO₄ Single crystals of Ca₂PbO₄ were prepared by flux technique and investigated by X-ray methods. It crystallizes with orthorhombic symmetry, space group D-Pbam. (a = 5.832; b = 9.766; c = 3.375 Å, Z = 2.) Ca₂PbO₄ belongs to the Sr₂PbO₄ type. It shows Ca²⁺ in a seven fold and Pb⁴⁺ in octahedral coordination.     

Die Kristallstruktur von Antimontetrachlorid-cyanurat [SbCl4NCO]3

The Crystal Structure of Antimony Tetrachloride Cyanurate [SbCl₄NCO]₃ [SbCl₄NCO]₃ crystallizes in the hexagonal space group P6₃/m with two formula units per unit cell; the lattice parameters are a = 1167 and c = 995 pm. The crystal structure was solved with X-ray diffraction data by means of a Patterson and a Fourier Synthesis and was refined by the method of least-squares to a reliability index of R = 3.6% for the 863 observed reflexions. The structure consists of [SbCl₄NCO]₃ molecules having the point symmetry 6 . The molecule is a derivate of cyanuric acid in a way such that each Sb atom is bonded in chelate manner by one N and one O atom; together with 4 Cl atoms the antimony attains a distorted octahedral coordination. The packing density in the crystal is not optimal, there exist cavities.