Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

Chloroantimonate(III): Die Kristallstruktur des 4,4′-Dipyridylium-pentachloroantimonats, (C10H8N2H2)SbCl5

Chloroantimonates(III): Crystal Structure of 4,4′-Dipyridylium Pentachloroantimonate, (C₁₀H₈N₂H₂)SbCl₅ (C₁₀H₈N₂H₂)SbCl₅ crystallizes in the triclinic space group P1 with a= 843.1(5), b = 958.6(8), c = 1098.0(10) pm, α = 112.45(6), β = 101.95(6), γ = 97.78(6)° and Z = 2. The structure is built up of 4,4 °-dipyridylium cations and pentachloroantimonate anions. The Sb atoms are distorted octahedrally coordinated. Mean distances are Sb? Cl = 242 pm (1×), Sb? Cl = 255 pm (2×), Sb ? Cl = 275 pm (2×) and Sb…?Cl.= 319 pm (1× ). The anions build up dimers.     

Kristallstruktur-Untersuchungen von Bis(pentafluorphenyl)tellurdihalogeniden (C6F5)2TeHal2 (Hal = Cl,Br)

Crystal Structure Determinations of Bis(pentafluorophenyl)tellurium Dihalides (C₆F₅)₂TeHal₂ (Hal = Cl, Br) Bis(pentafluorophenyl)telluriumdichloride and bis(pentafluorophenyl)telluriumdibromide crystallize at 10°C or 20°C from CH₂Cl₂ or CHCl₃ solution in the monoclinic space group P2₁/c with a = 649.5(1) pm, b = 1 275.6(2) pm, c = 1 816.2(5) pm, β = 92.89(2)° for (C₆F₅)₂TeCl₂ and a = 694.4(1) pm, b = 1 579.1(2) pm, c = 1 423.4(1) pm, β = 90.22(2)° for (C₆F₅)₂TeBr₂ with four formula units per each unit cell.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).     

Über die Decamethylferroceniumpolyiodide [(Me5C5)2Fe]Ix mit x = 3, 5 und 6,5. Darstellung und strukturelle Charakterisierung eines Triiodids (DMFc)I3, eines Pentaiodids (DMFc)I5 und eines Hexacosaiodids (DMFc)4I26

Studies on Polyhalides. 30 On Decamethylferriciniumpolyiodides [(Me₅C₅)₂Fe]I_x with x = 3, 5, 6.5: Preparation and Crystal Structures of a Triiodide (DMFc)I₃, a Pentaiodide (DMFc)I₅ and a Hexacosaiodide (DMFc)₄I₂₆ Decamethylferrocene (DMFc) may be oxidized by iodine analogous to ferrocene (Fc) to the decamethylferrocenium ion (DMFc)⁺ and precipitated as the crystalline solids decamethylferrocenium triiodide (DMFc)I₃, decamethylferrocenium pentaiodide (DMFc)I₅ and tetracisdecamethylferrocenium hexacosaiodide (DMFc)₄I₂₆. The two compounds with higher iodine content are new. These are characterized by X-ray diffraction methods on single crystals. The structures are built up from complex cations of expected geometry and isolated or remarkably connected polyiodide ions. Decamethylferrocenium triiodide C₂₀H₃₀FeI₃ crystallizes monoclinically in C2/m with a = 1489.9(4) pm, b = 1133.0(2) pm, c = 765.9(3) pm, β = 111.76(3)° and Z = 2. The crystal structure follows the CsCl-type and contains isolated triiodide ions of the linear symmetric form. Decamethylferrocenium pentaiodide C₂₀H₃₀FeI₅ crystallizes monoclinically in P2₁/c with a = 1130.0(2) pm, b = 1442.6(1) pm, c = 1716.6(2) pm, β = 96.62(1)° and Z = 4. The crystal structure may be deduced from the primitiv quadratic bundle of alternating cationic and anionic rods. It contains exceptionally isolated somewhat opened out pentaiodide ions. Tetrakisdecamethylferrocenium hexacosaiodide (C₂₀H₃₀Fe)₄I₂₆ crystallises monoclinically in P2₁/n with a = 1331.3(8) pm, b = 1319.4(4) pm, c = 3564(2) pm, β = 90.84(5)° and Z = 2. The crystal structure of this compound with unusual composition may be described as an inclusion compound with channels for the cations. The outstanding anionic grating may be derived from the primitive cubic lattice of iodide ions with iodine bridges on all edges by removing systematically 1/12 of the iodine molecules.     

Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

Tl5SnF9 und Tl5TiF9: die ersten [Tl5F3]2+‐Schichten in neuartigen Thallium(I)‐fluoridfluorometallaten(IV)

Tl₅SnF₉ and Tl₅TiF₉: The First [Tl₅F₃]²⁺ Layers in Novel Thallium(I) Fluoridefluorometallates(IV) Tl₅TiF₉ and Tl₅SnF₉ were prepared via solid state reactions from mixed powders of the TlF and SnF₄ or TiF₄, respectively, in platinum crucibles under Ar (573 K). Both fluorides are colourless, transparent and extremely hygroscopic. The compounds Tl₅MF₉ (M = Sn, Ti) crystallize in a new structure type in Pbam (Nr. 55) with a = 1117.6 pm, b = 684.8 pm, c = 799.2 pm for Tl₅SnF₉ and a = 1111.4 pm, b = 674.7 pm, c = 783.2 pm for Tl₅TiF₉. Characteristic building units in the new Thallium(I) fluoridefluorometallates(IV) are [Tl₅F₃]²⁺ sheets found for the first time, which are connected via [MF₆]^2– octahedra (M = Ti, Sn) to a threedimensional network (d_Sn–F = 194–197 pm, d_Ti–F = 186–187 pm). The monovalent Tl are coordinated by 8 F with distances Tl–F between 264 and 334 pm. The chemical bonding is discussed on the basis of Extended‐Hückel band structure calculations.     

Reaktionen von Lanthanoidhalogeniden mit Alkalibenzylverbindungen. Darstellung und Kristallstrukturen von [(tmeda)(C6H5CH2)2Y(μ-Br)2Li(tmeda)], [(tmeda)2SmBr(μ-Br)2Li(tmeda)] und [(dme)2SmBr(μ-Br)]2

Reactions of Lanthanide Halides with Alkalibenzyl Compounds. Synthesis and Crystal Structures of [(tmeda)(C₆H₅CH₂)₂Y(μ-Br)₂Li(tmeda)], [(tmeda)₂SmBr(μ-Br)₂Li(tmeda)] and [(dme)₂SmBr(μ-Br)]₂ Alkali-benzyl compounds react via a metathesis reaction with lanthanide halides to benzyl complexes of the rare earths. Reaction of [(C₆H₅CH₂)Li(tmeda)] with YBr₃ leads to the complex [(tmeda)Y(C₆H₅CH₂)₂ (μ-Br)₂Li(tmeda)] 1 , in which Yttrium and lithium are linked via two bromide bridges. However, the reaction of [(C₆H₅CH₂)Li(tmeda)] with SmBr₃ in toluene/tmeda leads under reduction of the Sm ion to the compound [(tmeda)₂SmBr(μ-Br)₂Li(tmeda)] 2 . 2 reacts with DME to yield the dimeric compound [(dme)₂SmBr(μ-Br)]₂ 3 . The structures of 1 – 3 were determined by X-ray single crystal structure analysis:

• 1: Space group P2₁/c, Z = 4, a = 829.5(6) pm, b = 1477.9(11) pm, c = 2575.0(10) pm, β = 92.03(6)°,
• 2: Space group P2₁, Z = 2, a = 954,7(3) pm, b = 1338.5(6) pm, c = 1244.9(5) pm, β = 107.51(3)°,
• 3: Space group P1 , Z = 1, a = 797.2(7) pm, b = 818.3(7) pm, c = 1169.7(8) pm, α = 100.96(6)°, β = 92.03(6)°, γ = 91.75(7)°.

     

Komplexchemie P-reicher Phosphane und Silylphosphane. III. Die Komplexverbindungen (t-Bu)3P9 · Cr(CO)5 und (t-Bu)3P9 · 2 Cr(CO)5 des Nonaphosphans(3), (t-Bu)3P9

Transition Metal Complexes of P-rich Phosphanes and Silyphosphanes. III. Complex Compounds (t-Bu)₃P₉ · Cr(CO)₅ and (t-Bu)₃P₉ · 2 Cr(CO)₅ Derived from Nonaphosphane (3) (t-Bu)₃P₉ The reaction of (t-Bu)₃P₉ 1 with Cr(CO)₅ · THF in a molar ratio of 1:1 yields (t-Bu)₃P₉ · Cr(CO)₅ 2 (yellow crystals) with the Cr(CO)₅ group coordinated to an equatorial P atom of the P₉ skeleton. In the reaction of 1 with 2 moles of Cr(CO)₅ · THF the complex product (t-Bu)₃P₉ · 2 Cr(CO)₅ 3 is formed with the second Cr(CO)₅ group linked to a basal P atom. Evidence for this comes from ³¹P NMR spectra as well as from crystal structure determinations of 2 and 3.2 crystallizes in the space group P2₁/n with a = 1012,9(2) pm, b = 2961,9(4) pm, c = 983,2(2) pm, β = 101,41(2)° and Z = 4 formula units. 3 crystallizes on the space group Pbcn with a = 2675,8(8) pm, b = 1222,4(2)pm, c = 2212,3 pm and Z = 8. In 2 and 3 the equatorial P atoms opposite to the P₂ dumbbell are complexed. The further complexation in 3 takes place at a basal P atom in Z-arrangement. The distances d(P Cr) are 243.5(1) pm and 240.5(1) pm and 240.5(1) pm for the equatorial P atoms in bf 2 and 3, respectively. For the basal P atom is 3 the distance in 235.7 pm. The P P distance range from 217.5 to 223.0 pm with the shorter ones at the bridgehead atom and the longer one at the P₂ dumbbell. The structures are discussed with that of the free ligand.     

Ag4Bi2O5 — ein neues Silberbismutat(III)

Ag₄Bi₂O₅ — A Novel Silverbismuthate(III) Yellow single crystals of Ag₄Bi₂O₅ have been obtained for the first time by solid state reaction of Ag₂O and Bi₂O₃ applying an oxygen pressure of 10 MPa at a temperature of 473 K. According to the results of a single crystal structure determination (Pnna, a = 1428.3(2), b = 569.2(1), c = 877.7(1) pm, Z = 4, 1544 diffractometer data, R₁ = 0.050, wR² = 0.094) the anionic partial structure of Ag₄Bi₂O₅ consists of chains of corner and edge sharing BiO₄-units. The silveratoms form a network of threedimensionally connected trigonal bipyramides with Ag? Ag-contacts between 285 and 323 pm.     

Erdalkali-Fluoromanganate(III): BaMnF5 · H2O und SrMnF5 · H2O

Alkaline Earth Fluoromanganates(III): BaMnF₅ · H₂O and SrMnF₅ · H₂O Solid BaF₂ or SrF₂ forms with solutions of Mn³⁺ in aqueous hydrofluoric acid precipitates of hitherto unknown BaMnF₅ · H₂ and SrMnF₅ · H₂O respectively. X-ray structure determination on single crystals of both isotypic compounds (space group P2₁/m, Z = 2; BaMnF₅ · H₂O: a = 537.0(3), b = 817.2(2), c = 628.0(4) pm β = 111.17(5)°, R_w = 0.035 for 1403 reflections; SrMnF₅ · H₂O: a = 510.8(1), b = 792.0(2), c = 610.6(1) pm, β = 110.24(1)° R_w = 0.068 for 539 reflections) reveal pure [MnF₆]^3? octahedra connected with each other to infinite chains by sharing trans corners. The H₂O molecules are coordinated to the alkaline earth ions only and form weak O? H…F hydrogen bonds. The pronounced weakening of the Mn? F bonds within the chain direction (Mn? F 2X 212.7(1)/210.8(5) pm, 2X 183.8(3)/181.8(9) pm, 2X 186.9(2)/187.2(8) pm) may be due by halves to the Jahn-Teller-effect as can be deduced by bond valence calculations.     

Die Kristallstrukturen von zwei Modifikationen von (C2H5)4NFel4

Crystal Structures of Two Modifications of (C₂H₅)₄NFeI₄ The crystal structures of two modifications, I and II, of (C₂H₅)₄NFeI₄ were determined from single crystal X-ray data. Modification I crystallizes in the tetragonal space group I4 m2 with a = 865.2(2), c = 1223.6(2) pm; II: orthorhombic, Pnnm, a = 1513.2(2), b = 1417.0(2), c = 843.5(1) pm. The crystal structures exhibit a different packing of the ions. In I the cubic close packing of the centers of gravity of anions and cations is the same as in the NaCl-type structure, in II the packing of the ions is similar to the NiAs-type structure. The Fe? I bond lengths were found to be 253.1 (I) and 254,0 pm (II) respectively.     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII [1]. Bildung und Struktur von [Li(DME)3]2{(SiMe3)[Cr(CO)5]2 P?PP?P[Cr(CO)5]2(SiMe3)}

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII. Formation and Structure of [Li(DME)₃]₂{(SiMe₃)[Cr(CO)₅]₂ P-P ? P-P[Cr(CO)₅]₂(SiMe₃)} Deep red crystals of the title compound 1 are produced in the reaction of LiP(Me₃Si)₂[Cr(CO)₅] with 1, 2-dibromoethane in DME. The structure of 1 was derived from the investigation of the ³¹P-NMR spectra and confirmed by a single crystal structure determination. 1 crystallizes in the space group P1 (no. 2); a = 1307.8(5)pm, b = 1373.1(5)pm, c = 1236.1(4)pm, α = 106.22(4)°, β = 88.00(3)°, γ = 115.52(4)° and Z = 1. 1 forms a salt composed of a dianion R₂R₄′P₄^2? (R ? SiMe₃, R′ ? Cr(CO)₅) and solvated Li⁺ cations. The zigzag shaped dianion possesses the symmetry 1 -C_i. The distances d(P? P) = 202.5(1)pm and d(P? P) = 221.9(1)pm correspond to a double bond and single bonds, respectively. The distances d(Cr? P) = 251.1(1) pm and 255.3(1) pm are larger than those observed so far which might be caused by the charge distribution in the dianion.     

Über Ethylmethyldiphenylammoniumpolyiodide (EtMePh2N)Ix mit x = 3, 5: Darstellung und strukturelle Charakterisierung eines Triiodids (EtMePh2N)I3 und eines Pentaiodids (EtMePh2N)I5

Studies on Polyhalides. 41. On Ethylmethyldiphenylammoniumpolyiodides (EtMePh₂N)I_x with x = 3, 5: Preparation and Crystal Structures of a Triiodide (EtMePh₂N)I₃ and a Pentaiodide (EtMePh₂N)I₅ So far unknown compounds (EtMePh₂N)I_x with x = 3 and 5 have been prepared and structurally characterized. The triiodide (EtMePh₂N)I₃ crystallizes monoclinically in C2/c with a = 3406.1(3) pm, b = 893.1(1) pm, c = 1222.7(1) pm, β = 99.24(1)° and Z = 8. The crystal structure contains cationic and two kinds of anionic layers alternating along [1 0 0]. One anionic layer is composed of triiodide ions forming the typical and widespread observed herring‐bone pattern. The other one contains zigzag chains (I^– · I₂) along [0 0 1] as a so far not observed structural motif. The pentaiodide (EtMePh₂N)I₅ crystallizes triclinically in P 1 with a = 1020.7(1) pm, b = 1023.1(1) pm, c = 1269.5(1) pm, α = 81.88(1)°, β = 72.66(1)°, γ = 60.65(1)° and Z = 2. The crystal structure is divided into along [0 1 1] alternating puckered cationic and anionic layers. The anions have the common shape of a V, but are here of the rare isolated type. From a topological view two pentaiodide ions are connected to chairlike decagonal rings which are concatenated along [0 1 1].     

Zur Kenntnis der Phasen A2−2xSn5+xCl12 (A = K,In)

On the A_2?2xSn_5+xCl₁₂ (A = K, In) Phases The refinement of the structure of A_2-2xSn_5+xCl₁₂ compounds (A = K⁺, In⁺) with single crystal data is reported. They crystallize with the Th₇S₁₂ type arrangement (a = 1192(2) pm, c = 428.9(8) pm (K-compound); a = 1189.8(6) pm, c = 431.2(3) pm (In-compound)) for which we propose the space group P6 . The possibility of meroedric twinning is discussed. Due to the composition of these compounds the structure is necessarily disordered and this leads to a wide range of homogeneity which can be influenced by the size and the polarity of the A type cation.     

Synthesis of Er5(BO3)2F9 and Properties of RE5(BO3)2F9 (RE = Er,Yb)

Er₅(BO₃)₂F₉ was synthesised under conditions of 3 GPa and 800 °C in a Walker‐type multianvil apparatus. The crystal structure was determined on the basis of single‐crystal X‐ray diffraction data, collected at room temperature. Er₅(BO₃)₂F₉ is isotypic to the recently synthesised Yb₅(BO₃)₂F₉ and crystallises in C2/c with the lattice parameters a = 2031.2(4) pm, b = 609.5(2) pm, c = 824.6(2) pm, and β = 100.29(3)°. The physical properties of RE₅(BO₃)₂F₉ (RE = Er, Yb) including high temperature behaviour and single crystal IR‐ / Raman spectroscopy were investigated.     

Dihalogen(pentafluorphenyl)sulfonium(IV)-hexafluoroarsenat C6F5SX2+AsF6− (X = Cl,Br) und Kristallstruktur von Di(pentafluorphenyl)sulfan (C6F5)2S

Dihalogen(Pentafluorophenyl)sulfonium(IV) Hexafluoroarsenate C₆F₅SX₂⁺AsF₆^? (X = Cl, Br) and Crystal Structure of Di(pentafluorophenyl)sulfane (C₆F₅)₂S The preparation and spectroscopic characterisation of the halogensulfonium salts C₆F₅SCl₂⁺AsF₆^? and C₆F₅SBr₂⁺AsF₆^? is reported. The new salts are much more stable than their trifluoromethyl derivatives. In addition the crystal structure of (C₆F₅)₂S is reported. Space group P4₃2₁2, Z = 4, 478 unique observed diffractometer data, R_int. = 0.07, lattice constants: a = 569.0(5) pm, c = 3785.8(22) pm, V = 1225 times; 10^?30 m³.     

An Expected Calcium Carbido Borate Chloride: Ca9Cl8(BC2)2

Ca₉Cl₈(BC₂)₂ was obtained by solid state reaction of a mixture of CaCl₂, Ca, B and C. The structure was solved by single crystal X-ray structure determination. Ca₉Cl₈(BC₂)₂ crystallizes in the orthorhombic space group Cmcm (No. 63, a = 1162.91(8) pm, b = 1341.59(10) pm and c = 1208.62(9) pm, Z = 4). The most striking element of the title compound is the bent BC₂^5– unit that is surrounded by a bicapped trigonal prismatic arrangement of calcium ions.     

Tetrafluoroaurate(III) der Lanthaniden M2F[AuF4]5 (M = Tb,Dy, Ho,Er)

Tetrafluoroaurates(III) of Lanthanoides M₂F[AuF₄]₅ (M = Tb, Dy, Ho, Er) Tetrafluoroaurates(III) M₂F[AuF₄]₅ with M = Tb, Dy, Ho, Er, all yellow, have been obtained. From single crystal data they crystallize triclinic, space group P1 -C¹_i (No. 2) with Tb: a = 1 194,34(7) pm, b = 798,46(6) pm, c = 902,02(7) pm, α = 89,033(7)°, β = 88,990(6)°, γ = 89,006(7)°; Dy: a = 1 191,66(9) pm, b = 796,33(8) pm, c = 899,65(9) pm, α = 88,956(8)°, β = 89,056(8)°, γ = 88,972(8)°; Ho: a = 1 189,06(10) pm, b = 795,46(6) pm, c = 896,81(7) pm, α = 88,912(8)°, β = 89,101(7)°, γ = 88,873(8)°; Er: a = 1 185,20(40), b = 793,98(14), c = 893,83(20), α = 88,751(23)°, β = 89,187(26)°, γ = 88,884(9)°