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.     

Spektroskopische und kristallographische Charakterisierung von [Cl3PNPCl3][MoOCl4] und die Kristallstruktur von [Cl3PNPCl3][MoCl6]

Spectroscopic and Crystallographic Characterization of [Cl₃PNPCl₃][MoOCl₄] and Crystal Structure of [Cl₃PNPCl₃][MoCl₆] [Cl₃PNPCl₃][MoCl₆] was obtained by reaction of MoCl₅ with [Cl₃PNPCl₃]Cl or [Cl₃PNPCl₃][PCl₆]. Its crystal was determined by X-ray diffraction (R = 0.072 for 889 observed reflexions). Lattice parameters: a = 811.9, b = 2086, c = 1016 pm, β = 101.7°, space group P2₁/c, Z = 4. The [Cl₃PNPCl₃]⁺ ions have a similar structure as in Cl₃PNPCl₃ [PCl₆] with PNP angles of 139°, but the crystal structures of the two compounds are not isotypic. Partial hydrolysis of [Cl₃PNPCl₃][MoCl₆] yields [Cl₃PNPCl₃][MoOCl₄] which forms green, very moisture sensitive crystals. X-ray diffraction patterns of [Cl₃PNPCl₃][MoOCl₄] single crystals exhibit planes of diffuse scattered radiation perpendicular to c^*, which show the presence of a two-dimensional disorder. Additional sharp reflexions correspond to an averaged structure with the lattice parameters a = 1598.4, b = 1141.2 and c = 415.1 pm, Z = 2, space group Pba2. Refinement of the averaged     

Ca3Cl2CBN,eine Verbindung mit dem neuen Anion CBN4−

Ca₃Cl₂CBN, a Compound with the New CBN^4? Unit The new compound Ca₃Cl₂CBN was obtained from the reaction of Ca and CaCl₂ with CaCN₂, B and C or with BN and C, in sealed tantalum containers at 900°C. The crystal structure is related with the structure of Ca₃Cl₂C₃ whereas the C₃^4? units (C_2v symmetry) are substituted by isoelectronic CBN^4? anions (C_s symmetry): Ca₃Cl₂CBN, Pnma, a = 1 386.7(9) pm, b = 384.7(3) pm, c = 1 124.7(6) pm, Z = 4; R = 0.055, R_w = 0.036 for 380 independent intensities. The CBN^4? units are located between layers of Ca²⁺ that are interconnected by Cl^?. The bond angle (C? B? N) is 176° and bond distances are d_{C? B} = 144 pm and d_{B? N} = 138 pm, respectively.     

CsPdCl3 – eine Verbindung mit [Pd2Cl6]-Baugruppen und anorganischem Kation

CsPdCl₃ – A Compound with Isolated [Pd₂Cl₆] Groups and an Inorganic Cation The crystal structure of CsPdCl₃ has been characterized by X-ray powder diffraction methods. Meanwhile it was possible to isolate single crystals and to confirm the structure by single crystal X-ray investigations. CsPdCl₃ crystallizes orthorhombic in space group Ibam (No. 72) with a = 13.724(1), b = 10.579(1), c = 8.499(1) Å, and Z = 8. CsPdCl₃ is a compound with a dinuclear [Pd₂Cl₆]^2– group and a cesium cation. Formerly such groups are only found in combination with large “organic” cations so far.     

Inhibition ability of ionic liquid [Bmim][NO3], [Bmim][BF4], and [Emim][BF4] on spontaneous coal combustion

Journal of Thermal Analysis and Calorimetry - From TG result, [Bmim][BF4] has the best inhibition ability of spontaneous coal combustion to delay the initial temperature, maximum temperature, and...     

Ueber eine Verbindung des Sarkosins mit Chlorzink

Ohne Zusammenfassung     

Tl4Pd3Cl10 – eine Verbindung mit neuartiger [(PdCl2Cl2/2)4]4–‐Baugruppe

Tl₄Pd₃Cl₁₀ – A Compound with a New [(PdCl₂Cl_2/2)₄]^4– Group Single crystals of Tl₄Pd₃Cl₁₀ can be obtained by hydrothermal synthesis. They show tetragonal symmetry with lattice parameters a = 15.956(1) Å and c = 14.146(1) Å, Z = 8 and space group I42d (No. 122). The atomic arrangement of Tl₄Pd₃Cl₁₀ is explored by X‐ray crystal structure analysis. Tl₄Pd₃Cl₁₀ is the first example of a new structural type with a hitherto not isolated tetramer [(PdCl₂Cl_2/2)₄]^4– group.     

[MoNCl3(THF)]4 – ein Nitrido-Komplex mit gefaltetem Mo4N4-Achtring

[MoNCl₃(THF)]₄ – a Nitrido Complex with a Folded Mo₄N₄ Eight-Membered Ring Red moisture sensitive single crystals of [MoNCl₃(THF)]₄ ( 1 ) prepared from saturated solutions of CH₂Cl₂ were characterized by a crystal structure determination. Space group P 4 2₁c, Z = 2, lattice dimensions at –80 °C: a = b = 1291.2(1), c = 1116.3(1) pm, R = 0.0581. In 1 the molybdenum atoms are linked by nearly linear Mo≡N–Mo bridges with MoN distances of 167 and 216 pm, which corresponds with triple and single bonds. In trans position to the Mo≡N bond the THF molecule is bonded by its oxygen atom. Along the diagonal axis Mo…Mo 1 is folded with an aperture angle of 140° thus forming a butterfly structure.     

Triphenylphosphinimino‐triphenylstiboniumchlorid, [Ph3PNSbPh3Cl], und seine Reaktion mit FeCl3

[Ph₃PNSbPh₃Cl] ( 1 ) was prepared by oxidative addition of ClNPPh₃ to triphenylstibine in dichloromethane solution. The compound is characterized by IR spectroscopy and by an X‐ray structure determination. 1 crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. Lattice dimensions at 193 K: a = 925.3(1), b = 1777.2(1), c = 1825.5(1) pm, β = 94.07(1)°, R₁ = 0.0228. 1 forms monomeric molecules with tetrahedrally coordinated phosphorus and trigonal‐bipyramidally coordinated antimony atom, the atoms N and Cl being in axial positions. The bond lengths PN and SbN are 155.0(2) and 198.4(2) pm, respectively, the PNSb angle is 138.6(1)°. 1 reacts with iron trichloride to give the known phosphoraneiminato complex [FeCl₂(NPPh₃)]₂.     

Solubility of H2S in ionic liquids [hmim][PF6], [hmim][BF4], and [hmim][Tf2N]

The solubility of hydrogen sulphide in three ionic liquids, viz. 1-hexyl-3-methylilmidazolium hexafluorophosphate ([hmim][PF₆]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF₄]), and 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf₂N]), at temperatures ranging from 303.15 K to 343.15 K and pressures up to 1.1 MPa were determined. The solubility values were correlated using the Krichevsky–Kasarnovsky equation and Henry’s constants were obtained at different temperatures. Partial molar thermodynamic functions of solvation such as standard Gibbs free energy, enthalpy, and entropy were calculated from the solubility results. Comparison of the values obtained show that the solubility of H₂S in these three ionic liquids was in the sequence: [hmim][BF₄] > [hmim][PF₆] ≈ [hmim][Tf₂N].     

Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]

Bromoplumbates with One‐dimensional Polymeric and Isolated Anions: (Bzl₄P)₂[Pb₃Br₈], (Bzl₄P)₂[Pb₃Br₈(dmf)₂], (Bzl₄P)[PbBr₃], (Bzl₄P)₂[PbBr₄], and (Bzl₄P)₄[Pb₂Br₆][PbBr₄] PbBr₂ reacts with LiBr and (Bzl₄P)(PF₆) (Bzl = CH₂C₆H₅) in acetone to form a series of bromoplumbate complexes with compositions and structures depending on the conditions of reaction and crystallization. While the anions in (Bzl₄P)₂[Pb₃Br₈] ( 1 ) and (Bzl₄P)[PbBr₃] ( 2 ) are one‐dimensional polymers with penta‐ and hexacoordinated Pb atoms, the metal atoms in the mono‐ and dinuclear complex anions of (Bzl₄P)₂[PbBr₄] · 2acetone ( 3 · 2acetone) and (Bzl₄P)₄[Pb₂Br₆][PbBr₄] ( 4 ) bind to four bromo ligands. From DMF as a solvent (Bzl₄P)₂[Pb₃Br₈(dmf)₂] ( 1 b ) crystallizes with the same bromoplumbate structure as in 1 a , but with dmf ligands occupying the coordination sites vacant in 1 a . Upon radiation of compound 3 with ultraviolet light greenish yellow photoluminescence (emssion maximum at 547 nm) is observed. Crystallographic details see “Inhaltsübersicht”.     

Ionic Association of the Ionic Liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in Molecular Solvents

Considering the ionic nature of ionic liquids (ILs), ionic association is expected to be essential in solutions of ILs and to have an important influence on their applications. Although numerous studies have been reported for the ionic association behavior of ILs in solution, quantitative results are quite scarce. Herein, the conductivities of the ILs [C_nmim]Br (n=4, 6, 8, 10, 12), [C₄mim][BF₄], and [C₄mim][PF₆] in various molecular solvents (water, methanol, 1‐propanol, 1‐pentanol, acetonitrile, and acetone) are determined at 298.15 K as a function of IL concentration. The conductance data are analyzed by the Lee–Wheaton conductivity equation in terms of the ionic association constant (K_A) and the limiting molar conductance (Λ_m⁰). Combined with the values for the Br^? anion reported in the literature, the limiting molar conductivities and the transference numbers of the cations and [BF₄]^? and [PF₆]^? anions are calculated in the molecular solvents. It is shown that the alkyl chain length of the cations and type of anion affect the ionic association constants and limiting molar conductivities of the ILs. For a given anion (Br^?), the Λ_m⁰ values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the K_A values of the ILs decrease in organic solvents but increase in water as the alkyl chain length of the cations increases. For the [C₄mim]⁺ cation, the limiting molar conductivities of the ILs decrease in the order Br^?>[BF₄]^?>[PF₆]^?, and their ionic association constants follow the order [BF₄]^?>[PF₆]^?>Br^? in water, acetone, and acetonitrile. Furthermore, and similar to the classical electrolytes, a linear relationship is observed between ln K_A of the ILs and the reciprocal of the dielectric constants of the molecular solvents. The ILs are solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation. This information is expected to be useful for the modulation of the IL conductance by the alkyl chain length of the cations, type of anion, and physical properties of the molecular solvents.