Die Kristallstruktur von AlI3 2 Pl3: ein P2I5+ AlI4−

Crystal Structure of AlI₃ · 2 PI₃:P₂I₅⁺ AlI₄^? The crystal structure of the title compound was determined from single crystal X-ray data. P₂I₅⁺AlI₄^? crystallizes in the orthorhombic space group Pbca, a = 1 088.3, b = 1 827.3, c = 2 031.6 pm, V = 4040 · 10⁶ pm³, Z = 8. The P₂I₅⁺ and AlI₄^? ions are connected by weak iodine-iodine bonds (I? I distances between 343.5 and 376.3 pm). The mean P? I and Al? I bond lengths were found to be 240.9 and 252.9 pm respectively.     

SeBr3[AlBr4] und TeI3[AlI4] – zwei weitere Vertreter des SCl3[AlCl4]-Strukturtyps

SeBr₃[AlBr₄] and TeI₃[AlI₄] – two further Compounds in the SCl₃[AlCl₄] Structure Type The reaction of SeBr₄ and AlBr₃ in a closed glass ampoule at 150°C yields quantitatively SeBr₃[AlBr₄] in form of yellow moisture sensitive crystals. From Te, two equivalents of I₂, and AlI₃ one obtains TeI₃[AlI₄] in form of dark red, moisture sensitive crystals. Both compounds crystallize monoclinic in the space group Pc (SeBr₃[AlBr₄]: a = 670.7(7) pm, b = 663.9(5) pm, c = 1 428.6(2) pm, β = 101.21(9)°, TeI₃[AlI₄]: a = 731.9(1) pm, b = 730.8(1) pm, c = 1 565.5(3) pm, β = 102.01(2)°). They are isotypic and have the SCl₃[AlCl₄] structure type. The structures are built of tetrahedral AlX₄^? ions and of pyramidal EX₃⁺ ions (E = S, Se, Te; X = Cl, Br, I). The chalcogen atoms are additionally coordinated by halogen atoms of surrounding AlX₄^? ions, corresponding to a strongly distorted octahedral coordination EX₃₊₃.     

Die Kristallstrukturen von SeCl3 +SbCl6−, SeBr3+GaBr4−, PCl4+SeCl5− und (PPh4+)2SeCl42− · 2 CH3CN

Crystal Structures of SeCl₃⁺SbCl₆^?, SeBr₃⁺GaBr₄^?, PCl₄⁺SeCl₅^?, and (PPh₄⁺)₂SeCl₄^2? · 2 CH₃CN The crystal structures of the title compounds were determined by X-ray diffraction. SeCl₃⁺SbCl₆^?: Space group P2₁/m, Z = 4, structure determination with 1795 observed unique reflections, R = 0.022. Lattice dimensions at ?80°C: a = 940.9, b = 1066.3, c = 1234.9 pm, β = 102.79°. The compound forms ion pairs with the structure of a double octahedron with linked surfaces. SeBr₃⁺GaBr₄^?: Space group Pc, Z = 2, structure determination with 1461 observed unique reflections, R = 0.058. Lattice dimensions at ?60°C: a = 660.1, b = 655.3, c = 1431.3 pm, β = 101.177°. The compound crystallizes in the SCl₃[AlCl₄] lattice type. Between the ions there are two relatively short Se … Br? Ga contacts. PCl₄⁺SeCl₅^?: Space group Ima2, Z = 8, structure determination with 1757 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1651.6, b = 1201.2, c = 1166.4 pm. The SeCl₅^? ions are associated to chains via interionic Se? Cl … Se contacts along the crystallographic c-axis. (PPh₄⁺)₂SeCl₄^2? · 2CH₃CN: Space group P2₁/n, Z = 2, structure determination with 2578 observed unique reflections, R = 0.050. Lattice dimensions at ?80°C: a = 1288.5, b = 726.0, c = 2585.8 pm, β = 101.65°. The compound includes planar-tetragonal SeCl₄^2? ions, which almost meet D_4h symmetry.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [SbF2(NPEt3)]2 und [SbF(NPEt3)2]2 sowie von NMe4+SbF4−

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SbF₂(NPEt₃)]₂ and [SbF(NPEt₃)₂]₂ as well as of NMe₄⁺SbF₄^? The title compounds have been prepared from antimony trifluoride with the silylated phosphaneimine Me₃SiNPEt₃ and [NMe₄]F, respectively. They were characterized by IR spectroscopy and by crystal structure determinations. [SbF₂(NPEt₃)]₂ : Space group Pbca, Z = 8, structure determination with 1264 unique reflections, R₁ = 0.028 for reflections with I > 2σ(I). Lattice dimensions at ?80°C: a = 1284.8, b = 1162.4, c = 1380.4 pm. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of the NPEt₃^? ligands. [SbF(NPEt₃)₂]₂ : Space group P2₁/c, Z = 4, structure determination with 2270 unique reflections, R₁ = 0.029 for reflections with I > 2μ(I). Lattice dimensions at ?75°C: a = 815.8, b = 1121.2, c = 2068.5 pm, β = 101.09°. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of one of the two NPEt₃^? ligands. The other NPEt₃^? group is terminally connected. NMe₄⁺SbF₄^? : Space group P2₁/c, Z = 4, structure determination with 1503 unique reflections, R₁ = 0.069 for reflections with I > 2μ(I). Lattice dimensions at ?50°C: a = 539.80, b = 896.10, c = 1760.3 pm, β = 90.338°. The compound includes monomeric SbF₄^? ions with distorted Ψ-trigonal-bipyramidal environment of the antimony atoms.     

Über die Reaktionen von N-Chloracetonimin mit Molybdänpentachlorid und Wolframhexachlorid Die Kristallstruktur von Me2CNH2[MoOCl4]

Reactions of N-Chloroacetoneimine with Molybdenum Pentachloride and Tungsten Hexachloride. Crystal Structure of Me₂C?NH₂[MoOCl₄] WCl₆ reacts with N-chloroacetoneimine under elimination of chlorine and formation of pentachloro-isopropylideneimino-tungsten(VI), Cl₅W?N?CMe₂, a brown-black crystal powder, which was characterized by i.r. spectroscopy. MoCl₅ reacts in a similar way, although only a product mixture can be obtained. Partial hydrolysis of this mixture yields isopropylideneiminium-tetrachlorooxomolybdate(V), Me₂C?NH₂⁺[MoOCl₄]^?, of which the crystal structure was determined (2323 unique observed reflexions, R = 0.049). Space group P2₁/c, Z = 4, a = 878.6, b = 907.2, c = 1252.2 pm, β = 91.29°. The compound consists of Me₂C?NH₂⁺ ions with a planar arrangement of the skeletal atoms and a CN bond length of 126.7 pm and of dimeric, centrosymmetric anions [MoOCl₄]₂^2? having Mo atoms linked via asymmetric chloro bridges (MoCl distances 238.4 and 307.6 pm). The longer Mo? Cl contacts are located in the trans-positions of the terminal oxoligands (MoO distance 164 pm).     

Bi53+‐Polykationen in geordneten und plastischen Kristallen von Bi5[AlI4]3 und Bi5[AlBr4]3

Bi₅³⁺ Polycations in Ordered and Plastic Crystals of Bi₅[AlI₄]₃ and Bi₅[AlBr₄]₃ Dark‐red air‐sensitive crystals of pentabismuth‐tris(tetrabromoaluminate) Bi₅[AlBr₄]₃ and black crystals of Bi₅[AlI₄]₃ have been crystallized from melts of Bi, BiX₃ and AlX₃ (X = Br, I). X‐ray diffraction on a single crystal of Bi₅[AlI₄]₃ (T = 293(2) K; space group Pnma; a = 2143.6(3) pm, b = 1889.1(1) pm, c = 811.74(5) pm) revealed an ordered packing of Bi₅³⁺ trigonal bipyramids and [AlI₄]^? tetrahedra that corresponds to the PuBr₃ structure type. Contrary to the so far known Bi₅³⁺ polycations with accurate D_3h symmetry, the bismuth cluster found in Bi₅[AlI₄]₃ holds only C_s symmetry. The room temperature structure of the tetrabromoaluminate Bi₅[AlBr₄]₃, which is related to the AuCu₃ type, shows a dynamic disorder of the Bi₅³⁺ polycations (T = 293(2) K; space group ; a = 1766.2(3) pm). Slight cooling induces the transition into an ordered rhombohedral phase isostructural to Bi₅[AlCl₄]₃ (T = 260(2) K; space group a = 1241.5(8) pm, c = 3041(2) pm).     

Untersuchungen an Polyhalogeniden. XVII. Darstellung und Kristallstruktur von Urotropiniumtriiodid,UrHI3

Studies on Polyhalides. 17. Preparation and Crystal Structure of Urotropinium Triiodide, UrHI₃ Urotropinium triiodide C₆H₁₃N₄I₃ is formed by the reaction of equimolar amounts of urotropinium iodide and iodine in ^tBuOH as red-brown cube-like crystals melting at 402 K under decomposition. The compound crystallizes monoclinically in the space group P2₁/c with a = 952.0(3) pm, b = 1 160.2(6) pm, c = 1 149.9(4) pm, β = 92.22(3)° and Z = 4. The till now not described crystal structure (R = 0.027 for 1 860 observed reflexes) contains urotropinium ions UrH⁺ and slightly distorted triiodide ions I₃^?(d(I—I) = 292.3(1), 294.1(1) pm, φ(I—I—I) = 178.27(2)°) which are linked to ion pairs by a rather short contact (d(I …? I) = 389.0(1) pm, φ(I—I …? I) = 149.12(2)°).     

Phosphanimin- und Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BF3(Me3SiNPEt3)], [BCl2(NPPh3)]2, [BCl2(NPEt3)]2, [B2Cl3(NPEt3)2]+BCl4− und [B2Cl2(NPiPr3)3]+BCl4−

Phosphaneimine and Phosphoraneiminato Complexes of Boron. Synthesis and Crystal Structures of [BF₃(Me₃SiNPEt₃)], [BCl₂(NPPh₃)]₂, [BCl₂(NPEt₃)]₂, [B₂Cl₃(NPEt₃)₂]⁺BCl₄^?, and [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? The title compounds have been prepared from the corresponding silylated phosphaneimines and boron trifluoride etherate and boron trichloride, respectively. The compounds form white moisture sensitive crystals, which were characterized by ¹¹B-nmr-spectroscopy, IR-spectroscopy and by crystal structure determinations. [BF₃(Me₃SiNPEt₃)] : Space group P2₁/c, Z = 4, R = 0.032 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1361.0, b = 819.56, c = 1422.5 pm, β = 109.86°. The donor acceptor complex forms monomeric molecules with a B? N bond length of 157.8 pm. [BCl₂(NPPh₃)]₂ · 2 CH₂Cl₂ : Space group P2₁/c, Z = 2, R = 0.049 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1184.6, b = 2086.4, c = 843.0 pm, β = 96.86°. The compound forms centrosymmetric dimeric molecules in which the boron atoms are linked to B₂N₂ four-membered rings with B? N distances of 152.7 pm via μ₂-N bridges of the NPPh₃ groups. [BCl₂(NPEt₃)]₂ : Space group Pbca, Z = 4, R = 0.029 for reflections with I > 2σ(I). Lattice dimensions at ?90°C: a = 1269.5, b = 1138.7, c = 1470.3 pm. The compound has a molecular structure corresponding to the phenyl compound with B? N ring distances of 151.0 pm. [B₂Cl₃(NPEt₃)₂]⁺BCl₄^? : Space group Pbca, Z = 8, R = 0.034 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1309.3, b = 1619.8, c = 2410.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 155.1 and 143.1 pm via the μ₂-N atoms of the NPEt₃ groups. [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? · CH₂Cl₂: Space group Pna2, Z = 4, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1976.5, b = 860.2, c = 2612.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 153.7 and 150.5 pm via the μ₂-N atoms of two of the NPⁱPr₃ groups. The third NPⁱPr₃ group is terminally connected to the sp²-hybridized boron atom with a B? N distance of 133.5 pm and with a B? N? P bond angle of 165.3°.     

(PPh4)2[V2Cl9][VCl5] · CH2Cl2 Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[V₂Cl₉][VCl₅] · CH₂Cl₂. Synthesis, I.R. Spectrum, and Crystal Structure The title compound was obtained by addition of CCl₄ to a solution of PPh₄Cl and excess VCl₄ in CH₂Cl₂. It forms black crystals which are light and moisture sensitive. The i.r. spectrum is reported. The crystal structure was determined by X-ray diffraction (3044 independent reflexions, R = 0.063). Crystal data: triclinic, space group P1 , Z = 2, a = 1186, b 1325, c = 1995 pm, α 97.5, β 105.6°, γ 93.4°. The structure consists of PPh₄⁺ cations, V₂Cl₉? and VCl₅? anions and CH₂Cl₂ molecules. The V₂Cl₉? ions consist of face-sharing octahedra with a long V…?V distance of 333 pm; the VCl₅? ions form nearly ideal trigonal bipyramids with V? Cl bonds of 228 pm (axial) and 218 pm (equatorial). Both anions deviate only marginally from D_3h symmetry. Half of the cations is arranged to (PPh₄⁺)₂ pairs about inversion centers.     

Kristallstrukturen von MgCr2O4-Typ Li2VCl4 und Spinell-Typ Li2MgCl4 und Li2CdCl4

Crystal Structures of MgCrO₄-type Li₂VCl₄ and Spinel-type Li₂MgCl₄ and Li₂CdCl₄ The crystal structures of the ternary lithium chlorides Li₂MCl₄ (M = Mg, V, Cd) have been determined firstly by X-ray single-crystal experiments. Li₂MgCl₄ and Li₂CdCl₄ crystallize in an inverse spinel structure (space group Fd3 m, Z = 8, a = 1 040.1(2) and 1 062.06(9) pm, structural parameters u = 0.25699(2) and 0.2550(1), R = 1.7 and 3.7% for 218 and 211 unique reflections). The Li? Cl distances of the tetrahedrally coordinated Li⁺ ions are significantly greater than calculated with Shannon's crystal radii ( > 238 ± 1 instead of 233 pm). Contrary to the results of X-ray powder data reported in the literature, Li₂VCl₄ crystallizes in the distorted spinel structure of MgCr₂O₄ type (space group F4 3m, Z = 8, a = 1 037.49(2) pm, R = 5.9% for 217 unique reflections). The decrease of the site symmetry of the octahedrally coordinated ions (V²⁺, Li⁺) from 3 m to 3m resulting in contracted and widened tetrahedral M₄ entities of the spinel structure is obviously caused by V? V metal—metal bonds (shortest V? V distance 366.2(7) pm).     

Die Kristallstruktur von Tetraphenylarsonium-tetrabromooxotechnetat(V), (Ph4As)TcOBr4

The Crystal Structure of Tetraphenylarsonium-tetrabromooxotechnetate(V), (Ph₄As)TcOBr₄ (Ph₄As)TcOBr₄ has been prepared from (Bu₄N)TcO₄, HBr and (Ph₄As)Br. The crystal structure of the complex has been determined by X-ray diffraction using MoKα radiation. The crystals are tetragonal, space group P 4/n with a = 1276.6(1) pm, c = 803.2(1) pm, Z = 2. The refinement based on 1595 reflexes converged to R = 0.034. The structure consists of discrete TcOBr₄^? anions and Ph₄As⁺ cations. The technetium is coordinated in a square pyramidal environment. A C_4v symmetry was derived for the complex anion. With this, it is isomorphous to the other structurally studied (Ph₄As)TcYX₄ complexes (Y = O, N; X = Cl, Br). The Tc = O length is 161.3(9) pm with Tc? Br 246.0(1) pm     

Rb6LiPr11Cl16[SeO3]12: Ein chloridisch derivatisiertes Rubidium‐Lithium‐Praseodym(III)‐Oxoselenat(IV)

Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂: A Chloride‐Derivatized Rubidium Lithium Praseodymium(III) Oxoselenate(IV) Transparent green square platelets with often truncated edges and corners of Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂ were obtained by the reaction of elemental praseodymium, praseodymium(III,IV) oxide and selenium dioxide with an eutectic LiCl–RbCl flux at 500 °C in evacuated silica ampoules. A single crystal of the moisture and air insensitive compound was characterized by X‐ray diffraction single‐crystal structure analysis. Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂ crystallizes tetragonally in the space group I4/mcm (no. 140; a = 1590.58(6) pm, c = 2478.97(9) pm, c/a = 1.559; Z = 4). The crystal structure is characterized by two types of layers parallel to the (001) plane following the sequence 121′2′1. Cl^? anions form cubes around the Rb⁺ cations (Rb1 and Rb2; CN = 8; d(Rb⁺?Cl^?) = 331 – 366 pm) within the first layer. One quarter of the possible places for Rb⁺ cations within this CsCl‐type kind of arrangement is not occupied, however the Cl^? anions of these vacancies are connected to Pr³⁺ cations (Pr4) above and below instead, forming square antiprisms of [(Pr4)O₄Cl₄]^9? units (d(Pr4?O) = 247–249 pm; d(Pr4?Cl) = 284–297 pm) that work as links between layer 1 and 2. Central cations of the second layer consist of Li⁺ and Pr³⁺. While the Li⁺ cations are surrounded by eight O^2? anions (d(Li?O5) = 251 pm) in the shape of cubes again, the Pr³⁺ cations are likewisely coordinated by eight O^2? anions as square antiprisms (for Pr1, d(Pr1?O2) = 242 pm) and by ten O^2? anions (for Pr2 and Pr3), respectively. The latter form tetracapped trigonal antiprisms (Pr2, d(Pr2?O) = 251–253 pm and 4 × 262 pm) or bicapped distorted cubes (Pr3, d(Pr3?O) = 245–259 pm and 2 × 279 pm). The non‐binding electron pairs (“lone pairs”) at the two crystallographically different Ψ¹‐tetrahedral [SeO₃]^2? anions (d(Se⁴⁺?O^2?) = 169–173 pm) are directing towards the empty cavities between the layer‐connecting [(Pr4)O₄Cl₄]^9? units.     

Synthese,Eigenschaften und Struktur von LiAuI4 und KAuI4 mit einer Diskussion der kristallchemischen Verwandtschaft zwischen den Halogenoauraten RbAuCl4, AgAuCl4, RbAuBr4 und LiAuI4

Synthesis, Properties, and Structure of LiAuI₄ and KAuI₄ with a Discussion of the Crystal Chemical Relationship between the Halogenoaurates RbAuCl₄, AgAuCl₄, RbAuBr₄ and LiAuI₄ The alkalimetal iodo aurates(III) MAuI₄ (M ? Li, K) are obtained in form of single crystals from MI, Au and I₂ in a sealed glass ampoule by heating to 550°C and slow cooling to 300°C. KAuI₄ crystallizes in the monoclinic space group P2₁/c with a = 968.6(4); b = 704.5(2), c = 1393.2(7) pm; β = 100.95(2)° and Z = 4. The crystal structure is built up from square planar AuI₄^? anions and K⁺ cations. The cations are coordinated by eight I atoms of neighbouring AuI₄^? anions with distances K? I between 350.0 and 369.6 pm. At 100°C KAuI₄ is reduced to form K₃Au₃I₈, which at 180°C decomposes to KI, Au and I₂ LiAuI₄ forms black, moisture sensitive needles, decomposing in the absence of iodine at 20°C to LiI, Au and I₂. It crystallizes in a variant of the RbAuBr₄ type structure with the space group P2₁/a and a = 1511.7(4); b = 433.9(4); c = 710.0(2) pm; β = 121.50(2)°; Z = 2. The crystal chemical relationship between the structures of RbAuCl₄, RbAuBr₄, AgAuCl₄ and LiAuI₄ is discussed.     

Synthese und Kristallstrukturen der Polytelluridokomplexe (PPh4)4[M2Te12] von Kupfer(I) und Silber(I)

Syntheses and Crystal Structures of the Polytellurido Complexes (PPh₄)₄[M₂Te₁₂] of Copper(I) and Silver(I) The title compounds have been prepared as black crystal needles by reactions of Na₂Te₃ with CuCl and AgNO₃, respectively, in dimethylformamide in the presence of PPh₄Br. With regard to the large cell dimensions the crystal structure determinations were done by an imaging plate instrument. (PPh₄)₄[Cu₂Te₁₂]: Space group P2₁/n, Z = 6, 51 338 detected reflections, structure determination with 14 177 unique reflections with I > 4σ(I), R = 0.081. Lattice dimensions at ? 50°C: a = 1 704.5, b = 1 694.5, c = 5 044 pm, β = 94.20°. (PPh₄)₄[Ag₂Te₁₂]: Space group P2₁/n, Z = 6, 80 811 detected reflections, structure determination with 16 092 unique reflections with I > 3σ(I), R = 0.052. Lattice dimensions at ? 50°C: a = 1 703.8, b = 1 722.9, c = 5 123 pm, β = 94.65°. The structures of the isotypic compounds consist of six symmetry independent PPh₄⁺ ions and two symmetry independent anions [M₂Te₁₂]^4?, in which the metal atoms of two (MTe₄)^?-fivering fragments are linked by a Te₄^2? chain.     

Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Formation of PPh₄[WOCl₄ · THF] and PPh₄Cl · 4As₄S₃ from W(CO)₆ and PPh₄[As₂SCl₅] and their Crystal Structures When W(CO)₆ and PPh₄[As₂SCl₅] are irradiated with UV light in tetrahydrofurane, PPh₄[WOCl₄ · THF], PPh₄ Cl· 4As₄S₃ and PPh₄[Cl₂H] are obtained. X-ray crystal structure determinations were performed. PPh₄[WOCl₄ · THF], monoclinic, space group P2₁/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh₄⁺ and [WOCl₄. THF]^? ions are present, the WOCl₄ group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh₄Cl · 4AsS₃, tetragonal, I4₁/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh₄⁺ and Cl^? ions and As₄S₃ molecules.     

Ternäre Halogenide vom Typ A3MX6. II. Das System Ag3−xNaxYCl6: Synthese,Strukturen, Ionenleitfähigkeit

Ternary Halides of the A₃MX₆ Type. II. The System Ag_3?xNa_xYCl₆: Synthesis, Structures, Ionic Conductivity . The influence of the substitution of Ag⁺ by Na⁺ ions on the crystal structure and the ionic conductivity of Ag₃YCl₆ (stuffed LiSbF₆-type structure) has been investigated. The system Ag_3?xNa_xYCl₆ forms a complete solid solution. The stuffed LiSbF₆-type structure is stable for all compositions. For compounds with Na⁺ contents of x > 1.67, the cryolite-type structure is observed as the high-temperature form. The transition temperature decreases steadily with increasing Na⁺ content. The “end member” phase Na₃YCl₆ transforms at 243 K from the monoclinic cryolite-type structure to the stuffed LiSbF₆-type structure (trigonal, R3 ; a = 697.3(1), c = 1 868.4(14) pm, Z = 3; R = 0.094; R_w = 0.069). The crystal structures of Ag_1.3Na_1.7YCl₆ (trigonal, R3 ; a = 691.5(2), c = 1 853.7(6) pm, Z = 3; R = 0.099, R_w = 0.081) and AgNa₂YCl₆ (trigonal, R3 ; a = 691.7(1), c = 1 853.9(5) pm, Z = 3; R = 0.099, R_w = 0.064) have also been determined. Both chlorides crystallize like Ag₃YCl₆ and Na₃YCl₆-I in the stuffed LiSbF₆-type structure. The monovalent cations, Ag⁺ and Na⁺, are distributed over the five octahedral voids that are occupied by the Ag⁺ ions alone in Ag₃YCl₆. The ionic conductivity for compounds within the solid solution Ag_3?xNa_xYCl₆ decreases with increasing Na⁺ content. The values for Na₃YCl₆ (σ = 1 · 10^?6 Ω^?1 cm^?1 at T = 500 K) are by 2.5 to 3.5 orders of magnitude smaller than those for Ag₃YCl₆ (σ = 6 · 10^?4 Ω^?1 cm^?1 at T = 500 K).     

Synthese und Kristallstruktur von [Se3N2Cl]+ GaCl4−

Synthesis and Crystal Structure of [Se₃N₂Cl]⁺GaCl₄^? [Se₃N₂Cl]⁺GaCl₄^? has been prepared by the reduction of [Se₂NCl₂]⁺GaC1₄^? with SbPh₃ in CH₂Cl₂ solution, forming red crystals, which were characterized by an X-ray structure determination. Space group P2₁/n, Z = 4, 1640 observed unique reflections, R = 0.050. Lattice dimensions at ? 80 °C: a = 929.4(1), b= 1078.8(1), c = 1135.7(1) pm, β = 92.026(9)°. The cations from nearly planar Se₃N₂ five membered rings with Se? N bond lengths from 170 to 176pm and a Se? Se bond of 242.2 pm. One of the selenium atoms is bonded to the chlorine atom.     

Dimethyl-N-Halogenamine,ihre Ammoniumsalze und Bortrihalogenid-Addukte

Dimethyl-N-Halogenoamine, their Ammonium Salts and Borontrihalide Adducts The preparation and vibrational spectra of (CH₃)₂NHCl⁺X^? (X^? = CF₃SO₃^? I , SO₃F^? II , SO₃Cl^? III , BCl₄^? IV ), and (CH₃)₂NHBr⁺CF₃SO₃^? V as well as the adducts (CH₃)₂NCl · S (S = BF₃ VI , BCl₃ VII , BBr₃ VIII ) and (CH₃)₂NBr · BF₃ IX are reported. The crystal structure of VII has been determined from three-dimensional diffractometer data at ?100°C. The Cl atom and one methyl group in the dimethyl-N-chloroamino group show disorder. The structural data are: B? Cl 183(2) pm, B? N 167(3) pm, N? C 152(3) pm (distances to disordered positions are not included).     

Eine Strukturvariante zum NaErCl4/α-NiWO4-Typ für ternäre Selten-Erd-Chloride vom Typ NaMCl4: Synthese und Kristallstruktur von NaLuCl4

A Structural Variant to the NaErCl₄/α-NiWO₄ Type for Ternary Rare-Earth Halides NaMCl₄: Synthesis and Crystal Structure of NaLuCl₄ Single crystals of NaLuCl₄ (orthorhombic, Pbcn (Nr. 60), Z = 4, a = 618.6(1) pm, b = 1 592.2(2) pm, c = 657.0(1) pm) were grown for the first time from the binary components using the Bridgman technique. The crystal structure may be derived from a hexagonally closest packing of Cl^? spheres with one half of all octahedral sites occupied by the cations Na⁺ and Lu³⁺, respectively. The close relation of the structure to that of NaErCl₄ (α-NiWO₄) is discussed. NaScCl₄ was found to be isotypic to NaLuCl₄.     

[Sb(NPPh3)4]+SbF6−: Synthese,Kristallstruktur und 121Sb-Mößbauer-Spektrum

[Sb(NPPh₃)₄]⁺SbF₆^?: Synthesis, Crystal Structure, and ¹²¹Sb Mössbauer Spectrum The title compound as well as the hexachloro antimonate [Sb(NPPh₃)₄]⁺SbCl₆^? have been prepared by the reaction of Me₃SiNPPh₃ with SbF₅ and SbCl₅, respectively, in acetonitrile solutions. The compounds form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy, by ¹²¹Sb Mössbauer spectroscopy, and by crystal structure analyses. A complete crystal structure analysis, however, could be carried out with [Sb(NPPh₃)₄]⁺SbF₆^? only. The compound crystallizes orthorhombically in the space group Pccn with four formula units per unit cell. The structure determination was done with 3 972 observed unique reflections, R = 0.053. Lattice dimensions at 19°C: a = 1 658,6; b = 1 698.9, c = 2 361.9 pm. In the cation [Sb(NPPh₃)₄]⁺ the antimony atom is tetrahedrally coordinated by the four nitrogen atoms of the phosphoraneiminato ligands with extremely short Sb? N bond lengths of 193 pm.