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.     

Über das Dimethyl(n-propyl)phenylammoniumtriiodid n-PrMe2PhNI3 und die Reihe der Dimethyl(isopropyl)phenylammoniumpolyiodide i-PrMe2PhNIx mit x = 3, 5, 7, 8, 9

Studies of Polyhalides. 35. On the Dimethyl(n-propyl)phenylammoniumtriiodide n-PrMe₂PhNI₃ and on the Series of Dimethyl(isopropyl)phenylammoniumpolyiodides i-PrMe₂PhNI_x with x = 3, 5, 7, 8, and 9 The new compounds n-PrMe₂PhNI₃ and i-PrMe₂PhNI_x with x = 3, 5, 7, 8 and 9 have been prepared by reaction of iodine I₂ with n-PrMe₂PhNI in EtOH and with i-PrMe₂PhNI in MeOH respectively. The crystal structures have been determined by single crystal X-ray diffraction methods. The triiodide n-PrMe₂PhNI₃ has a layerlike structure with alternating anionic and cationic layers. The similar, but not isotypic triiodide i-PrMe₂PhNI₃ may be described as a layerlike packing of asymmetric anions and tetraedral cations, too. The structure of the pentaiodide i-PrMe₂PhNI₅ consists of zig-zag like iodide-diiodine chains with additional iodine molecules attached to the iodide ions in trans position. The pentaiodide part of the heptaiodide ion in i-PrMe₂PhNI₇ forms meanderlike iodide-bis(diiodine) chains also with additional iodine molecules in trans position. The structure of the hexadecaiodide ion I₁₆^2– in the octaiodide i-PrMe₂PhNI₈ contains fourteen-membered rings, which are catenated by iodine molecules and linked to layers with ten- and two types of fourteen membered rings as meshes. The anionic iodine part of the enneaiodide i-PrMe₂PhNI₉ contains fourteen-membered rings, too, which are tied up by two iodine molecules forming in addition ten membered rings which are lined up alternately.     

Bulky Cations and Four different Polyiodide Anions in [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I12)

Black single crystals of [Lu(Db18c6)(H₂O)₃(thf)₆]₄(I₃)₂(I₅)₆(I₈)(I₁₂) were obtained from lutetium, I₂ and Db18c6 (dibenzo‐18‐crown‐6) in THF solution. In the bulky cation, Lu³⁺ is surrounded by nine oxygen atoms, six of Db18c6 and three of water molecules to which two THF molecules are attached each. Meanwhile, four polyiodide anions, (I₃)^–, (I₅)^–, (I₈)^2– and (I₁₂)^2–, in a 2:6:1:1 ratio form a three‐dimensional network and leave space for the bulky cations.     

Untersuchungen an Polyhalogeniden. XXVII. Über Tetra(n-propyl)ammoniumpolyiodide (n-Pr4N)In mit n = 3, 5, 7: Darstellung und strukturelle Charakterisierung eines Triiodids (n-Pr4N)I3, eines Pentaiodids (n-Pr4N)I5 und eines Heptaiodids (n-Pr4N)I7

Studies of Polyhalides. 27. On Tetra(n-propyl)ammonium Polyiodides (n-Pr₄N)I_n with n = 3, 5, 7: Preparation and Crystal Structures of a Triiodide (n-Pr₄N)I₃, a Pentaiodide (n-Pr₄N)I₅, and a Heptaiodide (n-Pr₄N)I₇ [(n-C₃H₇)₄N]I₃, [(n-C₃H₇)₄N]I₅ and [(n-C₃H₇)₄N]I₇ have been prepared by the reaction of tetra(n-propyl)ammoniumiodide [(n-C₃H₇)₄N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The triiodide is built up from layers of the quarternary ammonium ions n-Pr₄N⁺ and from two independent differently packed centrosymmetric triiodide ions I₃^? which alternate with each other along [100]. The pentaiodide ion forms slightly puckered almost squared nets perpendicular [001] of iodide ions which are connected with four iodine molecules by secondary bonds. The meshes from twelve iodine atoms include the cations. The centrosymmetric Z-shaped heptaiodide ion is built up from a linear symmetric triiodide ion and two iodine molecules forming twisted rope ladders along [001] which are separated by stacks of cations.     

Ein Netzwerk aus Iodid-Ionen und Iod-Molekülen in der Kristallstruktur von [Pr(Benzo-15-Krone-5)2]I21

A Three Dimensional Network of Iodide Ions and Iodine Molecules in the Crystal Structure of [Pr(Benzo-15-Crown-5)₂]I₂₁ Black polyhedra of [Pr(benzo-15-crown-5)₂]I₂₁ were grown from an ethanol / dichlormethane solution of PrI₃, benzo-15-crown-5 and I₂. The crystal structure (orthorhombic, P2₁cn, a = 1201.1(1), b = 2168.3(1), c = 2571.1(1) pm, Z = 4) is built up from sandwich like cations [Pr(benzo-15-crown-5)₂]³⁺ and polyiodide anions I₂₁^3-. This unique polyiodide anion exhibits a complex connection pattern of iodide ions and iodine molecules with variable bond lengths forming a complicated network.     

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.     

Piaselenol—Piaselenolium—Pentaiodid (C6H4N2Se · C6H5N2Se+I3− · I2), eine Struktur mit Polyiodid-schichten

Piaselenole—Piaselenolium—Pentaiodide (C₆H₄N₂Se · C₆H₅N₂Se⁺ I₃^? · I₂), a Structure with Polyiodide Layers The title compound crystallizes in the monoclinic space group P2₁/n with a = 9.320(3), b = 13.812(2), c = 17.159(3) Å, β = 96.11(2)°, V = 2196.3 ų, Z = 4. There occur no isolated I^5? anions but layer-shaped polyiodide aggregates built up by linear, asymmetric I₃^? anions and I₂ molecules. Almost linear triiodide chains are connected by I₂ molecules in a novel type of arrangement to form slightly puckered layers. The polyiodide layers contain several substructures known from other examples. The piaselenole and its conjugated acid, the piaselenolium cation, form a ribbon-like quasi-polymer in which the two components are alternating. They are connected in turns by a linear NH? N hydrogen bridge (N? N: 2.844 Å) and by a so called (SeN)₂-connectivity parallelogram, in which Se? N bonds and Se? N contacts are adjacent. Here we found a very short Se? N contact distance of 2.691 Å. The bond distances of piaselenole (Se? N: 1.787(3) Å, N? C: 1.318(5) Å, C? C: 1.453(8) Å) and also the angles are equal or similar to those occuring in other 1,2,5-selenadiazoles. The protonation of one N in the SeN₂ unit results in a loss of symmetry and significant changes in bonding distances and angles.     

[Ba(Benzo‐15‐Krone‐5)2](In)2: Darstellung und strukturelle Charakterisierung eines Triiodids (n = 3) und eines Heptaiodids (n = 7)

[Ba(benzo‐15‐crown‐5)₂](I₃)₂ and [Ba(benzo‐15‐crown‐5)₂](I₇)₂ can be obtained in crystalline form by reacting benzo‐15‐crown‐5 (C₁₄H₂₀O₅), barium iodide (BaI₂), and iodine (I₂) in ethan‐ole /dichloromethane. The triiodide consists of a sandwich‐like cation [Ba(benzo‐15‐crown‐5)₂]²⁺ and an isolated symmetrically linear I₃^‐ anion. The unusual I₇^‐ anion in the heptaiodide can be described as a V‐shaped pentaiodide unit, which is connected with a slightly widened iodine molecule to the rare Z‐form of the heptaiodide ion. In the crystal structure, secondary bonding distances lead to almost planar ten‐membered iodine rings, which are connected by common edges to form staircase‐like bands.     

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.     

Untersuchungen an Polyhalogeniden. XXII [1]. Dimethyldiphenylammoniumpolyiodide (Me2Ph2N)In mit n = 3, 13/3, 6, 8: Darstellung und strukturelle Charakterisierung eines Triiodids (Me2Ph2N)I3, Tridecaiodids (Me2Ph2N)3I13, Dodecaiodids (Me2Ph2N)2I12 und Hexadecaiodids (Me2Ph2N)2I16

Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me₂Ph₂N)I_n with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me₂Ph₂N)I₃, Tridecaiodide (Me₂Ph₂N)₃I₁₃, Dodecaiodide (Me₂Ph₂N)₂I₁₂, and Hexadecaiodide (Me₂Ph₂N)₂I₁₆ The new compounds [(CH₃)₂(C₆H₅)₂N]I₃, [(CH₃)₂(C₆H₅)₂N]₃I₁₃, [(CH₃)₂(C₆H₅)₂N]₂I₁₂ and [(CH₃)₂(C₆H₅)₂N]₂I₁₆ have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH₃)₂(C₆H₅)₂N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.     

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.     

Nontypical iodine–halogen bonds in the crystal structure of (3E)‐8‐chloro‐3‐iodomethylidene‐2,3‐dihydro‐1,4‐oxazino[2,3,4‐ij]quinolin‐4‐ium triiodide

Two kinds of iodine–iodine halogen bonds are the focus of our attention in the crystal structure of the title salt, C₁₂H₈ClINO⁺·I₃⁻, described by X‐ray diffraction. The first kind is a halogen bond, reinforced by charges, between the I atom of the heterocyclic cation and the triiodide anion. The second kind is the rare case of a halogen bond between the terminal atoms of neighbouring triiodide anions. The influence of relatively weakly bound iodine inside an asymmetric triiodide anion on the thermal and Raman spectroscopic properties has been demonstrated.     

Polymere Iodoplumbate – Synthese und Kristallstrukturen von (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF und (Me3N–C2H4–NMe3)2[Pb2I7]I

Polymeric Iodoplumbates – Synthesis and Crystal Structures of (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF, (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF, and (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ) and (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF ( 2 ) have almost the same composition, but completely different structures. Both compounds are formed selectively depending on the reaction and crystallization conditions. In 2 the Pb^II atoms are coordinated either by six bridging I^– ligands in the two-dimensional [Pb₅I₁₄]^4– network or by six DMF ligands in the [Pb(dmf)₆]²⁺ cations. In contrast, (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ) contains non-coordinating I^– anions between the iodoplumbate layers. The iodoplumbate anions in 2 and 3 consist of face and corner sharing PbI₆ octahedra, whereas in 1 PbI₆ and PbI₅(dmf) octahedra share common edges to form a one-dimensional polymeric section of the PbI₂ structure. (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ): Space group P1, a = 920.1(3), b = 1597.2(5), c = 1613.9(4) pm, α = 66.02(2), β = 84.53(2), γ = 85.99(2)°, V = 2156(1) · 10⁶ pm³; (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄]·DMF ( 2 ): Space group P2₁, a = 1201.21(9), b = 3031.1(2), c = 1294.96(9) pm, β = 108.935(7)°, V = 4459.8(5) · 10⁶ pm³; (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ): Space group Pnma, a = 2349.9(2), b = 1623.83(9), c = 980.75(7) pm, V = 3742.4(5) · 10⁶ pm³.     

Eine neue und unerwartete Form des Dodecaiodid-Ions I122–: Darstellung und Kristallstruktur des Bis[kalium(dibenzo-18-krone-6)]dodecaiodids [K(C20H24O6)]2I12

Studies of Polyhalides. 32. A New and Unforeseen Shape of the Dodecaiodide Ion I₁₂^2–: Preparation and Crystal Structure of Bis[potassium(dibenzo-18-crown-6)]dodecaiodide [K(C₂₀H₂₄O₆)]₂I₁₂ Particularly iodine rich polyiodides tend to form extended iodine nets by multiply concatenating iodide or triiodide ions through iodine molecules. Therefore the discovery of a not ramified, nearly isolated dodecaiodide ion I₁₂^2– in the new compound [K(C₂₀H₂₄O₆)]₂I₁₂ seems to be unexpected. This ion may be described as an extraordinary long fragment of the triiodide-iodine chain (I₃^– · I₂)_∞.     

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.     

Complex structure tri- and polyiodides of iodocyclization products of 2-allylthioquinoline

Iodocyclization products of 2-allylthioquinoline are obtained in the form of polyiodides with different stoichiometric compositions. X-ray crystallography data are analyzed for two different crystal structures of 1-iodomethyl-1,2-dihydro[1,3]thiazolo[3,2-a]quinolinium polyiodides: triiodide C₁₂H₁₁INS⁺I ₃ ^? and complex polyiodide 2(C₁₂H₁₁INS⁺I ₃ ^? )·I₂. A comparison is made of the nonbonding interactions of dihydrothiazoloquinolinium with atoms of the triiodide anion and complex polyiodide to show the crystal structure features attributed to the participation of molecular iodine.     

Bis(methyltri‐o‐tolylphosphonium) octaiodide

In the crystal structure of the title compound, 2C₂₂H₂₄P⁺·I₈²⁻, the I₈²⁻ anion is located on a crystallographic inversion centre and consists of two tri‐iodide anions linked by di‐iodine at angles of 89.92 (4)° to form a planar `Z'‐shaped dianion. The octaiodides are linked via long‐range interactions [3.877 (11) Å] into infinite polyiodide ribbons. This is the first example of a structure containing an [(o‐tolyl)₃PMe]⁺ cation, and the C_Me—P—C—C_Me torsion angles of −54.0 (11), −51.3 (11) and −48.2 (11)° indicate that the configuration is exo₃.     

Crystal and molecular structure of diphenyliodonium triiodide

A new salt diphenyliodonium triiodide (C₁₂H₁₀I₄) was obtained. The [C₁₂H₁₀I⁺][I₃⁻] compound was isolated as red brown crystals and studied by single-crystal X-ray diffraction. The structure of diphenyliodonium triiodide consists of separate, virtually linear I₃⁻ anions and C₁₂H₁₀I⁺ cations. Strong intermolecular anion-anion (I₃⁻…I₃⁻) and anion-cation (I₃⁻…I⁺) interactions in the crystal structure leads to a change in the symmetry of triiodide ions. The complex formation in the system organic cation iodide-elementary iodine was studied by spectrophotometry. The complex composition was found (1: 1), and the stability constant of the complex in chloroform was determined (loggB = 3.91).     

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].