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.     

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.     

Untersuchungen an Polyhalogeniden. XXIII. Kristallstrukturen der N-Alkylurotropiniumtriiodide UrRI3 mit R = Methyl,Ethyl, n-Propyl und n-Butyl

Studies on Polyhalides. 23. Crystal Structures of N-Alkylurotropinium Triiodides UrRI₃ with R = Methyl, Ethyl, n-Propyl, and n-Butyl The salts UrRI₃ may be prepared by the reaction of N-alkylurotropinium iodides UrRI with iodine I₂ at room temperature from aqueous solution. N-methylurotropinium triiodide C₇H₁₅N₄I₃ crystallizes monoclinically in P2₁/c with a = 1300.8(2) pm, b = 1276.0(3) pm, c = 859.3(2) pm, β = 94.75(2)° and Z = 4. The crystal structure is built up from layers of cations UrMe⁺ and of linear symmetric triiodide ions I₃^? alternating along [100]. N-ethylurotropinium triiodide C₈H₁₇N₄I₃ crystallizes orthorhombically in Pnma with a = 1397.3(5) pm, b = 1221.3(2) pm, c = 886.2(2) pm and Z = 4. The cationic (UrEt⁺) and anionic (I₃^?) layers alternate along [0 10]. N-propylurotropinium triiodide C₉H₁₉N₄I₃ crystallizes monoclinically in P2₁/c with a = 1885.7(5) pm, b = 1657.1(5) pm, c = 1700.5(4) pm, β = 112.39(2)° and Z = 12. The three independent cations and anions are slightly, but differently distorted. N-butylurotropinium triiodide C₁₀H₂₁N₄I₃ crystallizes monoclinically in P2₁/m with a = 991.8(3) pm, b = 757.8(2) pm, c = 1128.2(2) pm, β = 90.73(2)° and Z = 2. The crystal structure is stacked by alternating cationic and anionic layers along [001]. The triiodide ion is asymmetric and linear.     

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].     

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)°).     

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.     

Untersuchungen an Polyhalogeniden III. Tetrammin-kupfer(II)-tetraiodid, [Cu(NH3)4I2 · I2], und Tetrammin-kupfer(II)-hexaiodid, [Cu(NH3)4I3]I3

Studies on Polyhalides. III. Crystal Structures of [Cu(NH₃)₄I₂ · I₂] and [Cu(NH₃)₄I₃]I₃ Tetramminecopper(II)tetraiodide [Cu(NH₃)₄I₂ · I₂] (I) crystallizes monoclinically in the space group C2/m with a = 1 185.9 pm, b = 892.8 pm, c = 656.8 pm, β = 111.10° and Z = 2 formula units. Tetramminecopper(II)hexaiodide [Cu(NH₃)₄I₃]I₃ (II) crystallizes orthorhombically in the space group Pnnm with a = 874.9 pm, b = 1 089.8 pm, c = 885.3 pm, and Z = 2 formula units. A special feature of these structures are coordinated polyiodide ions I₄^2? (I) or I₃^? (II). In both compounds four coplanar nitrogen atoms and two axial iodine atoms form a quasi-octahedral coordination around copper with the usual (4+2)-tetragonal distortion. The copper ions are connected by linear, centrosymmetric polyiodide ions I₄^2? (I) or I₃^? (II). Therefore infinite planar zigzag chains of units [Cu(NH₃)₄I₄] (I) or [Cu(NH₃)₄I₃]⁺(II) are resulting. The counterion I₃^? (II) is intercalated between these chains.     

New Fluoromanganate(III) Hydrates: Mn3F8 · 12H2O and AgMnF4 · 4H2O

Single crystals of fluoride hydrates Mn₃F₈ · 12 H₂O and AgMnF₄ · 4 H₂O have been prepared and characterized by X-ray methods. Mn₃F₈ · 12 H₂O crystallizes in the space group P1 (a = 623.0(3), b = 896.7(4), c = 931.8(4) pm, α = 110.07(2)°, β = 103.18(2)°, γ = 107.54(2)°, Z = 1); AgMnF₄ · 4 H₂O crystallizes in the space group P2₁/m (a = 700.9(2), b = 726.1(1), c = 749.4(3) pm, β = 107.17(3)°, Z = 2). Both structures contain Jahn-Teller-distorted [Mn(H₂O)₂F₄]^? anions as well as crystal water molecules and exhibit a complex hydrogen bond network between anions and cations, i. e. [Mn(H₂O)₆]²⁺ for the first and a polymeric [Ag(H₂O)₂]^? cation for the second compound.     

Formation and Crystal Structure of the Salt (IC(PPh3)2)2I[I3]·(I2)2 with a new Polyiodide Chain

The reaction of the carbodiphosphorane Ph₃P=C=PPh₃ ( 1 ) with MeI in the presence of iodine gives the oxidation product (IC(PPh₃)₂)₂I[I₃]·(I₂)₂ ( 2 ). In the solid state dimeric units linked by indefinite ···I^?···I₂···I₃^?···I₂···I^?··· chains are found. An additional I···I contact between the cation and the I₂ molecule is formed, amounting to 359.23(5) pm. 2 crystallizes in the monoclinic space group P2/c, with the unit cell dimensions a = 2053.9(1), b = 1011.4(1), c = 1889.8(1) pm; β = 105.21(1)° and Z = 4.     

Phosphaniminato-Komplexe des Iods. Synthese und Kristallstrukturen von Ph3PNIO2 und Ph3PNSiMe3 · I2

Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph₃PNIO₂ and Ph₃PNSiMe₃ · I₂ Ph₃PNIO₂ has been prepared as yellow crystals by the reaction of Ph₃PNSiMe₃ with I₂O₅ in boiling acetonitrile, whereas the molecular complex Ph₃PNSiMe₃ · I₂ is formed as brown crystals by the reaction of Ph₃PNSiMe₃ with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations. Ph₃PNIO₂: Space group P2₁/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond. Ph₃PNSiMe₃ · I₂: Space group P1 , Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I₂ molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N? I? I axis with a bond length N? I of 243.2 pm.     

Darstellung sowie Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrogenfluorid, (C6H5)3PO · HF

Preparation, Crystal and Molecular Structure of Triphenylphosphineoxide Hydrogen - fluoride (C₆H₅)₃PO · HF (C₆H₅)₃PO · HF was prepared from hydrofluoric acid (40%) and (C₆H₅)₃PO in benzene. It crystallizes in the monoclinic space group P2₁/c with a = 1 032.8(3), b = 1 051.0(7), c = 1695.5(2) pm, β = 121.95(2)° and Z = 4; d (calc./obs.) 1.27/1.26 g ° cm^?3. The structure was determined by direct methods from 2 709 independent reflections and has been refined by full matrix least squares methods to R = 0.049. In the compound HF and (C₆H₅)₃PO are linked by a short H-bond. Some distances: O? F 238.4(5), O? H 142.3, H? F 99.8, P? O 149.5(4) pm. Angle O? H? F 159.8°.     

Die Pyridinaddukte der Goldhalogenide. 3. Darstellung,Eigenschaften und Kristallstruktur zweier Modifikationen von AuBr · NC5H5

Pyridine Adducts of Gold Halides. 3. Preparation, Properties, and Crystal Structure of Two Modifications of AuBr · NC₅H₅ The reaction of AuBr · S(CH₂C₆H₅)₂ with pyridine in absolute ethanol yields the crystalline compound AuBr · pyridine. It crystallizes in the triclinic space group P1 with the lattice constants a = 791.5(2) pm, b = 935.6(2) pm, c = 1005.1(3) pm, α = 85.78(2)°, β = 102.07(2)°, γ = 109.31(2)°. When the solvent is toluene, monoclinic crystals are formed with the space group C2/c and a = 1225.9(2) pm, b = 1522.2(3) pm, c = 1459.7(3) pm, β = 97.82(2)°. The triclinic structure is built up by Au₄ zig-zag chains AuBr₂—Au(py)₂—Au(py)₂—AuBr₂, whereas the monoclinic phase contains infinite chains with the sequence AuBr₂—Au(py)₂. In each case the linkage is formed by weak Au—Au-interactions.     

Untersuchungen über Iodoferrate: Die Kristallstrukturen von Fe(THE)6(FeI3THF)2 · THF und Fe(Ch2O)6(FeI4)2 · I2(THF = C4H8O)

Investigations about Iodoferrates: The Crystal Structures of Fe(thf)₆(FeI₃thf)₂ · thf and Fe(CH₂O)₆(FeI₄)2 · I₂(thf = C₄H₈O) The crystal structures of FeI₂ · 3 thf (i.e. Fe(thf)₆(FeI₃thf)₂ · thf) ( 1 ) and Fe(CH₂O)₆(FeI₄)₂ · I₂ ( 2 ) were determined from single crystal X-ray data. 1 crystallizes in the cubic space group Pa3, a = 1759.8 pm, Z = 4, 2 in the monoclinic space group P2₁/n, a = 997.4, b = 1669.4, c = 1082.6 pm, β = 93.11°, Z = 2. The structure of 1 is composed of octahedral Fe(thf)₆²⁺ cations and distorted tetrahedral [FeI₃(thf)]-anions (Fe? I distance 261.1 pm). In 2 two tetrahedral tetraiodoferrate (III) anions are linked by an iodine molecule. The Fe? I distance was found to be 253.9 pm (mean, the I? I distance between FeI₄^? and I₂ 356.1 pm. The decomposititon of 1 in vacuum at elevated temperatures and the resulting formation of 2 from 1 are discussed.     

Bildung siliciumorganischer Verbindungen. 94. Die Kristallstruktur des Hexaphenyltrisilacyclohexans Si3C39H36

Formation of Organosilicon Compounds. 94. Crystal Structure of Hexaphenyltrisilacyclohexane Si₃C₃₉H₃₆ 1.1.3.3.5.5-Hexaphenyl-1.3.5-trisilacyclohexane crystallizes monoclinically in the space group P2₁/n (No. 14) with a = 1718.3 pm, b = 1769.2 pm, c = 1091.4 pm, β = 90.72° and Z = 4 molecules per unit cell. The trisilacyclohexane sceleton is present in a flattened twist boat conformation with mean bond angles of 110.0° at the Si atoms and 117.9° at the C atoms, respectively. The mean bond lengths are d(Si? C) = 187.1 pm in the six membered ring and 187.9 pm to the substituents.     

Die Molekül‐ und Kristallstruktur des Rubidium(Dibenzo‐18‐Krone‐6)‐pentaiodids [Rb(C20H24O6)]I5

Molecular and Crystal Structure of Rubidium(dibenzo‐18‐crown‐6)pentaiodide [Rb(C₂₀H₂₄O₆)]I₅ [Rb(Dibenzo‐18‐crown‐6)]₂(I₅)₂ is obtained as dark brown columns by reacting dibenzo‐18‐crown‐6, rubidium iodide, and iodine in a molar ratio of 1 : 1 : 6 in ethanole / dichlormethane (1:1). [Rb(C₂₀H₂₄O₆)]₂(I₅)₂ crystallizes with four formula units per unit cell in the orthorhombic space group Pnma with a = 1725.15(2) pm, b = 1863.76(3) pm and c = 1885.19(3) pm. The crystal structure consists of pentaiodide units I₅^—, which are linked to one another by head‐to‐tail‐contacts. The I₂ units, which stick out of the chain, are twisted against each other, in a way that neither a cis or a trans configuration is formed. By secondary bonding, the iodine atoms form nets of 18‐member planar rings with an almost rectangular form. This net‐like structural element has not been described up to now.     

Über die Kristallstrukturen von CH3PF2H+AsF6− und CH3PF2H+SbF6− und eine einfache Darstellung von CH3PF2

On the Crystal Structures of CH₃PF₂H⁺AsF₆^? and CH₃PF₂H⁺SbF₆^? and a simple Method for Preparation of CH₃PF₂ A simple method for preparation of CH₃PF₂ from CH₃PCl₂ is reported. The phosphonium salts CH₃PF₂H⁺MF₆^? are obtained by the reaction of CH₃PCl₂ with superacidic systems HF/MF₅ (M = As, Sb). CH₃PF₂H⁺SbF₆^? crystallizes in the space group P1 with a = 548.4(4) pm, b = 695.5(8) pm, c = 960.2(9) pm, α = 94.68(5)°, β = 97.19(6)°, γ = 94.41(6)° and Z = 2. CH₃PF₂H⁺SbF₆^? crystallizes in P1 with a = 554.3(3), b = 724.2(4), c = 970.4(5), α = 94.73(4)°, β = 96.14(5)°, γ = 95.30(4)°.     

Untersuchungen an Natriumtrifluormethylsulfonat – Kristallstruktur und Phasenumwandlung des Monohydrats und Natriumionenleitfähigkeit des wasserfreien Salzes

Studies on Sodium Trifluormethanesulfonate – Crystal Structure and Phase Transition of Sodium Trifluormethanesulfonate Monohydrate and Sodium Ion Conductivity of Anhydrous Sodium Trifluormethanesulfonate According to the results of temperature dependent powder diffractometry (Guinier-Simon-technique) sodium trifluormethanesulfonate monohydrate is dimorphous. The phase transition occurs at ?35°C. The room-temperature modification crystallizes monoclinic in space group P2₁/c with the lattice parameters a = 941.6(5) pm, b = 654.3(2) pm, c = 1062.4(5) pm and β = 107.73(2)°. The crystal structure consists of double layers of trifluormethanesulfonate anions, the lipophilic CF₃-groups pointing at each other. Sodium is coordinated by four oxygen atoms from four different anions and by two molecules of crystal water. The resulting polyhedron may be addressed as a distorted octahedron. The low-temperature modification crystallizes orthorhombic in space group Pnma with the lattice parameters a = 645.31(9) pm, b = 538.03(9) pm, c = 1745.3(3) pm. The loss of crystal water occurs at 136°C. Anhydrous sodium trifluormethanesulfonate shows a phase transition at 252°C. The high-temperature modification is a good sodium ionic conductor (σ = 4.1 · 10^?1 Ω^?1 cm^?1 at 250°C).     

Synthese,Kristallstrukturen und thermisches Verhalten von Er2(SO4)3 · 8 H2O und Er2(SO4)3 · 4 H2O

Syntheses, Crystal Structures, and Thermal Behavior of Er₂(SO₄)₃ · 8 H₂O and Er₂(SO₄)₃ · 4 H₂O Evaporation of aqueous solutions of Er₂(SO₄)₃ yields light pink single crystals of Er₂(SO₄)₃ · 8 H₂O. X-ray single crystal investigations show that the compound crystallizes monoclinically (C2/c, Z = 8, a = 1346.1(3), b = 667.21(1), c = 1816.2(6) pm, β = 101.90(3)°, R_all = 0.0169) with eightfold coordination of Er³⁺, according to Er(SO₄)₄(H₂O)₄. DSC- and temperature dependent X-ray powder investigations show that the decomposition of the hydrate follows a two step mechanism, firstly yielding Er₂(SO₄)₃ · 3 H₂O and finally Er₂(SO₄)₃. Attempts to synthesize Er₂(SO₄)₃ · 3 H₂O led to another hydrate, Er₂(SO₄)₃ · 4 H₂O. There are two crystallographically different Er³⁺ ions in the triclinic structure (P 1, Z = 2, a = 663.5(2), b = 905.5(2), c = 1046.5(2) pm, α = 93.59(3)°, β = 107.18(2)°, γ = 99.12(3)°, R_all = 0.0248). Er(1)³⁺ is coordinated by five SO₄^2– groups and three H₂O molecules, Er(2)³⁺ is surrounded by six SO₄^2– groups and one H₂O molecule. The thermal decomposition of the tetrahydrate yields Er₂(SO₄)₃ in a one step process. In both cases the dehydration produces the anhydrous sulfate in a modification different from the one known so far.     

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.     

Neue Polyiodide des Caesiums mit Doppel‐ und Tripeldecker‐Kationen, [Cs(Benzo‐18‐Krone‐6)2]Ix und [Cs2(Benzo‐18‐Krone‐6)3](Ix)2 (x = 3, 5)

New Polyiodides of Cesium containing Double and Triple Decker Cations, [Cs(benzo‐18‐crown‐6)₂]I_x and [Cs₂(benzo‐18‐crown‐6)₃](I_x)₂ (x = 3, 5) [Cs(b18c6)₂]I_x (x = 3 (1) , 5 (3) ) and [Cs₂(b18c6)₃](I_x)₂ (x = 3 (2) , 5 (4) ) (b18c6 = benzo‐18‐crown‐6) have been synthesized by the reaction of benzo‐18‐crown‐6 (C₁₆H₂₄O₆), cesium iodide (CsI) and iodine (I₂) in acetonitrile ( 1 ), ethanol/dichloromethane ( 2 , 4 ) and 2‐methoxyethanol ( 3 ). Their crystal structures were determined on the basis of single crystal X‐ray data {( 1 ): monoclinic, C2/c, Z = 4, a = 2048.8(5), b = 1329.5(5), c = 1588.7(5) pm, β = 110.23(1)°; ( 2 ): monoclinic, C2/c, Z = 4, a = 2296.0(1), b = 2092.7(1), c = 1373.6(1) pm, β = 100.21(1)°; ( 3 ): monoclinic, P2₁/n, Z = 4, a = 1586.3(1), b = 1745.5(1), c = 1608.6(1) pm, β = 92.37(1)°; ( 4 ): triclinic, , Z = 2, a = 1241.7(1), b = 1539.8(2), c = 1938.4(2) pm, α = 91.15(1), β = 100.53(1), γ = 95.26(1)°}. As expected, double decker cations centered by Cs atoms, [Cs(b18c6)₂]⁺, are found in the structures of ( 1 ) and ( 3 ). In contrast, the triple decker cation found in ( 2 ) and ( 4 ) is less common. The triiodide anions of ( 1 ) and ( 2 ) can be regarded as normal and the chain‐type pentaiodide anions of ( 3 ) and ( 4 ) fall into the known systematic sequence of these anions. The differences in the connectivity of the crystallographically independent I₅^? anions in ( 4 ) are surprising with respect to the fact that, so far, independent pentaiodide anions do not show variations in their scheme of connectivity within one crystal structure.