Kristallstrukturbestimmung von N-Trimethylsily-N′-methylimidazoliumbromid

Crystal Structure Determination of N-Trimethylsilyl-N′-Methylimidazolium Bromide The reaction of Trimethylbromosilane and N-Methylimidazole (NMI) led to a 1:1 compound stable at room temperature. The reaction was carried out at room temperature and colorless single crystals were obtained by sublimation. The addition compound crystallizes in the orthorhombic space group Pbnb (No. 56) with lattice constants a = 1218.3(2)pm, b = 1333.6(1)pm, c = 1360.2(2)pm, Z = 8, D_calc = 1.414 g/cm³. For 1506 independent reflections, measured at 21°C the structure could be refined to R = 0.067 and R_w = 0.062.     

Synthesis and Structure of Ba12F19Cl5

A new member belonging to the binary phase diagram of BaF₂ and BaCl₂ was synthesized. The single domain crystals of Ba₁₂F₁₉Cl₅ can be prepared from a nonstoichiometric flux with molar ratio of 1 : 1 between BaFCl and BaF₂. The compound crystallizes at room temperature in the non-centrosymmetric hexagonal space group P6 2m with a = b = 1408.48(14) and c = 427.33(5) pm. Three different barium environements with coordination number of nine are found. The barium fluorine distances vary between 250.59(6) – a short distance compared to other Ba? F distances – and 302.7(1) pm and barium chlorine distances between 331.55(3) and 336.19(15) pm. This compound is further characterized using Raman spectroscopy.     

Die Kristallstrukturen von α- und β-K3OCl

The Crystal Structures of α- and β-K₃OCl The orange coloured compound K₃OCl has been prepared. It exists in a low temperature modification (α-K₃OCl) and a high temperature modification (β-K₃OCl). The transition temperature is 364 ± 5 K. The crystal structures were determined by x-ray diffraction. α-K₃OCl crystallizes at room temperature in the orthorhombic space group Pbnm (Z = 4) with the cell parameters a = b = 723.9(2) pm and c = 1 027.7(2) pm in the anti-GdFeO₃-structure type. The high temperature modification β-K₃OCl crystallizes (Z = 1) in the cubic space group Pm3m in the β-Ag₃SI-structure type with a = 516.2(2) pm (T = 393 K).     

Existiert eine Wurtzit‐Modifikation von Lithiumbromid? — Untersuchungen im System LiBr/LiI —

Is there a Wurtzite‐Modification of Lithium Bromide? — Studies on the System LiBr/LiI — Deposition of mixtures of LiBr/LiI (ratio: LiBr/LiI = 3:1, 2:1, 1:1, 1:2, 1:3, 1:4) and of pure LiI and LiBr from the gas phase onto a sapphire substrate at ‐196 °C in a high vacuum chamber were investigated by means of temperature‐dependent X‐ray diffraction. Below 0 °C LiI crystallizes in the hexagonal Wurtzite‐modification (β‐LiI) with a = 451.4(1) und c = 731.1(2) pm, which transforms into the cubic rock salt modification (α‐LiI, a = 602.57(3) pm) by heating up to room temperature. Co‐depositions of LiBr/LiI formed solid LiBr_1‐xI_x solutions that also crystallize in the Wurtzite‐modification, below room temperature. Compared to β‐LiI, these solid solutions are more stable and transform into the cubic phase at the significantly higher temperature of 80 °C. The lattice constants of LiBr_1‐xI_x with x ≈ 0.7 are a = 445.48(7), c = 719.1(1) pm and with x ≈ 0.4 are a = 431.50(5), c = 691.7(1) pm. The hexagonal phase LiBr_1‐xI_x is observed for the complete series of mixed crystals with 0.25 ≤ x ≤ 0.8. Both cubic phases, α‐LiI and LiBr, show solubilities of up to ca. 10 % of the respective other compound. In case of pure LiBr only the cubic modification (a = 551.54(2) pm, 25 °C) was observed in the complete temperature range (‐196 °C to 25 °C).     

Synthese und Struktur von zwei- und dreikernigen Heterometallkomplexen mit Nitridobrücken zwischen Re und Mo

Synthesis and Structure of Two- and Threenuclear Heterometallic Complexes with Nitrido Bridges between Re and Mo The reaction of ReNCl₂(PMe₂Ph)₃ with MoCl₄(NCEt)₂ yields the heterometallic threenuclear complex [{(Me₂PhP)₃(EtCN)ClRe≡N–}₂MoCl₄][MoNCl₅]. The anion [MoNCl₅]^2– presumably results from a transfer of the nitrido ligand from the Re to the Mo atom. The air-sensitive compound is paramagnetic with μ_eff = 2.87 B. M. at room temperature. A reduction of the magnetic moment to 1.74 B.M at 20 K starts at 140 K. The complex crystallizes in the orthorhombic space group Pca2₁ with a = 2430(1), b = 1328(1), c = 2436.3(2) pm, Z = 4. With bond angles Re–N–Mo of 164° and 167° the nitrido bridges are almost linear. The distances Re–N of 169 and 170 pm can be interpreted with triple bonds. The Mo–N bond lengths of 210 and 211 pm correspond to single bonds. In the anion [MoNCl₅]^2– the distance Mo≡N is 167 pm. Hydrolysis of the threenuclear complex results in a cleavage of one of the nitrido bridges to yield (Me₂PhP)₃(EtCN)ClRe≡N–MoOCl₄. The compound is paramagnetic with μ_eff = 1.71 B.M. at room temperature. It crystallizes in the orthorhombic space group Pbca with a = 1718.5(4), b = 2037(1), c = 2041.1(7) pm, Z = 8. In the dinuclear complex the [MoOCl₄]^– unit is only weakly coordinated to the nitrido ligand with Mo–N = 246.5 pm, while the distance of the Re≡N bond of 168.1 pm is almost unchanged in comparison with a terminal bond. The bond angle Re≡N–Mo is 165.6°.     

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.     

Untersuchungen an Polyhalogeniden. XVI. Darstellung und Kristallstrukturen der Bipyridiniumpolyiodide Bipy · HIn mit n = 3, 5 und 7

Studies on Polyhalides. 16. Preparation and Crystal Structures of Bipyridiniumpolyiodides Bipy · HI_n with n = 3, 5, and 7 With simply protonated α,α′-Bipyridyl Bipy · H⁺ a triiodide Bipy · HI₃, a pentaiodide Bipy · HI₅ and a heptaiodide Bipy · HI₇ may be prepared in the presence of iodide ions I^? and dependent of the iodine I₂ content. Bipyridiniumtriiodide C₁₀H₉N₂I₃ crystallizes at room temperature monoclinically in P2₁/n with a = 1 122.8(1) pm, b = 1 072.7(1) pm, c = 1 200.2(3) pm, β = 98.02(2)° and Z = 4. The crystal structure is built up from mixed cationic and anionic layers. Bipyridiniumpentaiodide C₁₀H₉N₂I₅ crystallizes at room temperature monoclinically in P2₁/c with a = 887.3(5) pm, b = 2 527.9(12) pm, c = 830.7(3) pm, β = 106.78(5)° and Z = 4. The crystal structure contains triiodide ions I₃^? till now uniquely connected by iodine molecules I₂ in a trigonal planar way. Bipyridiniumheptaiodide C₁₀H₉N₂I₇ crystallizes at room temperature triclinically in P&1macr; with a = 713.1(3) pm, b = 1 007.9(3) pm, c = 1 464,8(4) pm, α = 81.07(3)°, β = 89.92(3)°, γ = 82.77(3)° and Z = 2. The crystal structure contains a V-shaped pentaiodide ion I₅^? completed by an iodine molecule I₂ to a trigonal pyramidally shaped heptaiodide ion I₇^? and at the same time connected to a zigzag chain.     

Über Münzmetall‐Quecksilber‐Chalkogenidhalogenide. IV1) Hydrothermalsynthese und Kristallstruktur von CuHgSI und CuHg2S2I

On Coinage Metal Mercury Chalcogenide Halides. IV Hydrothermal Synthesis and Crystal Structure of CuHgSI and CuHg₂S₂I The hydrothermal reaction of CuI with α‐HgS in diluted aqueous HI‐solution as solvent at 180 °C yields dark red crystals of CuHgSI. The compound crystallizes orthorhombic in the space group Pna2₁ with a = 718.3(1) pm, b = 834.3(2) pm and c = 698.9(1) pm and Z = 4. CuHg₂S₂I was obtained by the hydrothermal reaction of CuI with α‐HgS in diluted HI‐solution at 300 °C as black crystals. The compound crystallizes orthorhombic in the space group Cmc2₁ with a = 1261.8(3) pm, b = 722.4(1) pm and c = 693.7(1) pm and Z = 4. Both crystal structures could be explained as distorted version of the Wurtzite structure type in which two different types of anion‐lattices are built up.     

NaNb6Cl15 – Preparation,Structure, Ionic Conduction

NaNb₆Cl₁₅ is prepared by heating Nb₃Cl₈, NaCl and Nb under Ar at 1 170 < T [K] < 1 270 forming black regular dodecahedra. It crystallizes in the cubic space group Ia3 d (a = 2 041.7(2) pm at room temperature) and transforms to a tetragonal structure below 150 K (probably I4₁/acd, a = 2 037.2(6), c = 2 028.2(2) pm at 80 K). The Na⁺ ions are at room temperature dynamically disordered in a split position. Their mobility is investigated by IR spectroscopy and electrochemical methods.     

Untersuchungen an Polyhalogeniden. XXVI [1]. Über N-Propylurotropiniumpolyiodide UrPrIx mit x = 5 und 7: Strukturelle Charakterisierung eines Pentaiodids und eines Heptaiodids

Studies on Polyhalides. 26. On N-Propylurotropinium Polyiodides UrPrI_x with x = 5 and 7: Crystal Structures of a Pentaiodide and a Heptaiodide The salts UrPrI_x with x = 5 and 7 are formed by the reaction of N-propylurotropinium iodide UrPrI with excess iodine I₂ at room temperature from aqueous solution. N-propylurotropinium pentaiodide C₉H₁₉N₄I₅ crystallizes monoclinically in P2₁/n with a = 1007.6(3) pm, b = 1362.5(3) pm, c = 2899.0(9) pm, β = 91.49(3)º and Z = 8. The crystal structure is built up from parallel chains of cations UrPr⁺ and pairs of V-shaped pentaiodide anions I₅^? along [0 1 0]. N-propylurotropinium heptaiodide C₉H₁₉N₄I₇ crystallizes triclinically in P1 with a = 970.4(1) pm, b = 971.1(1) pm, c = 1357.8(2) pm, α = 106.83(1)º, β = 92.28(1)º, γ = 105.17(1)º and Z = 2. The crystal structure is stacked by alternating cationic and anionic double layers along [0 0 1]. The heptaiodide layer shows a two-dimensional network.     

Untersuchungen an Polypseudohalogeniden. 3. Darstellung und Kristallstruktur von Kaliumdicyanoiodat(I)-Diiminooxalsäurediethylester (1/1), K[I(CN)2] · C6H12N2O2

Studies on Polypseudohalides. 3. Preparation and Crystal Structure of K[I(CN)₂] · C₆H₁₂N₂O₂ The new compound K[I(CN)₂] · C₆H₁₂N₂O₂, C₈H₁₂IKN₄O₂, may be prepared by reaction of an aqueous solution of potassium cyanide and an ethanolic solution of iodine cyanide at 255 K. The direct formation from the components potassium cyanide, iodine cyanide and diimino oxalic acid diethyl ester is possible in different solvents, too. The compound has been investigated by chemical analysis, spectroscopic methods and structural analysis based on single crystal X-ray data. At room temperature it crystallizes in the triclinic space group P1 (No. 2) with a = 428.5 pm, b = 925.9 pm, c = 1035.0 pm, α = 63.41°, β = 76.33°, γ = 78.58° and Z = 1. The compound may be described as a solvated salt built up by a potassium ion, a trihalide-analogous dicyanoiodate(I)-ion and a molecule C₆H₁₂N₂O₂. The anion (point symmetry 1 ) is nearly linear. The distance d(I? C) = 230.2 pm is lengthened compared with the corresponding distance in iodine cyanide. The geometry of the for the first time characterized molecule diimino oxalic acid diethyl ester is as expected. The crystal structure can be interpreted as a sequence of ionic and molecular layers along [0 1 0].     

Die ungewöhnliche Umwandlung von P(SnMe3)3 in P4(SnMe2)6

The Unusual Transformation of P(SnMe₃)₃ to P₄(SnMe₂)₆ The stannylated phosphine P(SnMe₃)₃ reacts in the presence of small amounts of [(ZnCl)₂Fe(CO)₄(THF)₂] in THF (tetrahydrofurane) at room temperature forming insoluble P₄(SnMe₂)₆ ( 1 ). This compound crystallizes as colourless needles directly from the reaction mixture (space group Cmcm, a = 1593.6(3) pm, b = 1118.2(2), c = 1602.5(3), Z = 4). Reaction of ZnCl₂ with P(SnMe₃)₃ under the same reaction conditions leads to the complex [ZnCl₂{P(SnMe₃)₃}THF] ( 2 ) (space group Pccn, a = 1593, 6(3) pm, b = 1118, 2(2), c = 1602, 5(3), Z = 8.     

Kristallstruktur und Phasenumwandlungen von As(CH3)4I

Crystal Structure and Phase Transitions of As(CH₃)₄I The crystal structure of α-As(CH₃)₄I at room temperature was determined using single crystal data: cubic, space group Pa3 , a = 1 198.0(2) pm. Therefore α-As(CH₃)₄I displays a novel crystal structure, which is not comparable to known AB-Typ structures with respect to the arrangement of anions and the baricenters of the complex cations. Differential thermal analysis showed three phase transitions at 103, 175 and 215°C. The lattice parameters of the high temperature phases (temperature dependent Guinier measurements) are: β-As(CH₃)₄I (tetragonal): a = 845.2(2) pm, c = 615.0(2) pm; γ-As(CH₃)₄I (hexagonal): a = 737.7(2) pm, c = 1 082.2(3) pm; and to δ-As(CH₃)₄I (hexagonal): a = 705.8(2) pm, c = 1 147(1) pm. β-and γ-As[(CH₃)]₄I are isotypic to N(CH₃)₄Cl and As(CH₃)₄Br, respectively.     

Synthesis and Crystal Structure of [Fe(Cp)2]3(Bi2Cl9)·thf

Single crystals of [Fe(Cp)₂]₃(Bi₂Cl₉)·thf were obtained from a thf solution containing ferrocene and BiCl₃. The structure shows disorder at room temperature which disappears upon cooling, coupled with a decrease in symmetry. The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ [a = 1698.64(2), b = 2318.69(3), c = 1085.66(2) pm] with three ferrocenium ions, one nonachlorodibismutate ion and one molecule of thf in the asymmetric unit.     

Kristallstruktur,Leitfähigkeit und magnetische Suszeptibilität von Er2Te3

Crystal Structure, Conductivity, and Magnetic Susceptibility of Er₂Te₃ Via a chemical vapour transport reaction with ErCl₃ as transporting agent, single crystals of Er₂Te₃ up to a size of 1.5 mm are available. X-ray structure analysis revealed for the compound the Sc₂S₃-type with the space group Fddd and the lattice parameters a = 1212.7(2) pm, b = 858.1(2) pm and c = 2572.8(4) pm (Z = 16). According to measurements of the fundamental absorption (DRIFT) the compound is a semiconductor with a band gap of 0.77(5) eV. Magnetic susceptibility measurements revealed paramagnetic behaviour in the temperature range 5–300 K with μ_p = 9.07 B.M. and θ_p = –4.3 K.     

Struktur,Verzwillingung und Eigenschaften von Ce4Br3C4

Structure, Twinning, and Properties of Ce₄Br₃C₄ The new compound Ce₄Br₃C₄ can be prepared from Ce metal, CeBr₃ and C (3 : 3 : 2) at 1020 °C. It crystallizes in P 1 with a = 422.7(1) pm, b = 1103.4(3) pm, c = 1126.8(2) pm, α = 77.15(3)°, β = 90.13(2)° and γ = 84.42(3)°. The crystals are characteristically twinned, the twin law being (1 0 0, ¹/₂ –1 0, 0 0 –1). The crystal structure contains puckered layers of edge sharing Ce₆C₂ octahedra. The mean C–C distance in the C₂ units is 133(5) pm. Ce₄Br₃C₄ has at room temperature a specific resistivity of 100 mΩ cm and an effective magnetic moment of 2.55(3) μ_B (Ce³⁺).     

(Meta)stabiles CaC2

(Meta)stable CaC₂ One out of four modifications of CaC₂ is the so‐called metastable Calcium Carbide, CaC₂‐III, which was synthesized as pure material. It forms by heating monoclinic CaC₂‐II (C2/c) above 150 °C and remains stable after cooling down to room temperature. The structure was refined from X‐ray powder patterns (C2/m, Z = 4, a = 722.6(1) pm, b = 385.26(7) pm, c = 737.6(1) pm, β = 107.345(2)°). After grinding CaC₂‐III transforms back into CaC₂‐II. Heating CaC₂‐III induces a reversible phase transition into the cubic modification (CaC₂‐IV) at 460 °C. Differences between the three different structures of CaC₂ I–III, being stable at ambient conditions are also shown by ¹³C‐MAS‐NMR measurements, especially the presence of two distinct types of carbon atoms in the structure of the title compound.     

Low-temperature crystal growth of Cs2LiLuCl6-II and Cs2KScCl6 under reducing conditions and their structural refinement

Cs₂LiLuCl₆ (form II, metastable at room temperature) and Cs₂KScCl₆ were obtained as single crystals from reaction of CsLu₂Cl₇: Li = 1:1 and Cs₃Sc₂Cl₉: K = 1:2 in arc-welded tantalum tubes at 500°C. They crystallize with the cubic face-centered K₂NaAlF₆-type structure (elpasolite, Fm3m, Z = 4) with a = 1040.9 pm, x(Cl) = 0.2483(4) [Cs₂LiLuCl₆-II] and a = 1087.3(3) pm, x(Cl) = 0.2263(6) [Cs₂KScCl₆].     

Untersuchungen an Polyhalogeniden. XI. Darstellung und Kristallstruktur des Diethylmethylphenylammoniumtriiodids,Et2MePhNI3

Studies on Polyhalides. 11 Preparation and Crystal Structure of Diethylmethylphenylammoniumtriiodide, Et₂MePhNI₃ Diethylmethylphenylammoniumtriiodide C₁₁H₁₈NI₃ crystallizes at room temperature monoclinically with a = 824.1(2) pm, b = 1 428.5(2) pm, c = 1 430.0(2) pm, β = 103.17(3)° and Z = 4. The crystal structure is build up from layers of the quarternary ammonium ions Et₂MePhN⁺ and of the triiodide ions I₃^?, which alternate with each other along [1 0 0]. The packing of these layers and of the groups within each layer seems to be particularly effective without forming noticeable short contact distances.