Inhaltsiibersicht. Urotropiniumtriiodid CsH,,N41, fallt bei der 92,22(3)O und Z = 4. Die bisher nicht beschriebene Kristall-Umsetzung aquimolarer Mengen Urotropiniumiodid und Iod struktur (R = 0,027 fur 1 860 beobachtete Reflexe) enthalt aus 'BuOH in rotbraunen wurfelahnlichen Kristallen an, die Urotropiniumionen UrH + und geringfugig verzerrte 'Modidbei 402 K unter Zersetzung schmelzen. Die Substanz kristalli-ionen 13-(d(l-I) = 292,3(1), 294,1(1) pm, p(1-1-1) = siert in der monoklinen Raumgruppe P2& rnit a = 178,27(2)"), die uber einen kurzen Kontakt Ionenpaare bilden 952,0(3) pm, b = 1 160,2(6) pm, c = 1 149,9(4) pm, fi = (d(1-* I) = 389,0(1) pm, p(1-I * * -I) = 149,12(2)"). Studies on Polyhalides. 17. Preparation and Crystal Structure of Urotropinium Triiodide, UrHI, Abstract. Urotropinium triiodide C6HI3N4I3 is formed by the and slightly distorted triiodide ions 13-(d(I-I) = 292.3(1), reaction of equimolar amounts of urotropinium iodide and 294.1(1) pm, p(1-1-1) = 178.27(2)") which are linked to ion iodine in 'BuOH as red-brown cube-like crystals melting at pairs by a rather short contact (d(1 . . . I) = 389.0(1) pm, 402 K under decomposition. The compound crystallizes p(1-I --. I) = 149.12(2)"). monoclinically in the space group P2,/c with a = 952.0(3) pm, b = 1160.2(6)pm, c = 1149.9(4)pm, fi = 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+

Aminobenzenes, XI')Alkylation of 1,3,5-Tripyrrolidinobenzene 1,3,5-Tripyrrolidinoben~ne (1) reacts with alkyl halides through an SN2 reaction to give cyclohexadienylium halides (o-complexes) 2, 7, or 10, which are model substances for electrophilic aromatic substitution in a manner analogous to the Meisenheimer-compounds for nucleophilic aromatic substitution. They can be deprotonated with bases to produce the alkylbenzenes 4,8, or 13. N-Alkylation is observed simultaneously with C-alkylation except for benzyl bromides which show only C-alkylation to2f-kand7a -c,respectively. -Underthereactionconditionsemployed for C-alkylation a preceding N-alkylation can be excluded. The lower homologues (C, and C,) of the o,o'-dibromo-n-alkanes react through an initial C-alkylation and a subsequent intramolecular N-reaction to produce indolinium 9 a and quinolinium bromides 9b, respectively. The higher homologues (C4, C5, and Clo) lead to a coupling of two tripyrrolidinobenzenes 1 by C,C-(lo), C,N-(1 1) and N,N-alkylation (12).

The new compound [(Crypt-2.2.2)H2]I8 has been prepared by the reaction of [(Crypt-2.2.2)H2](I3)2 with iodine in methanol. It crystallizes in the orthorhombic space group Pbcn with a = 11.476 (2), b = 13.589 (2), c = 22.888 (2) Å and Z = 4. The crystal structure has been refined to RF = 0.031 for 1618 reflections. It may be described as a layerlike packing of octaiodide anions I82-and diprotonated 2.2.2-Crypt as cations. The non planar octaiodide anion is built up from two triiodide groups and a bridging iodine molecule.Tris(1, 10-phenanthroline)nickel(II) octaiodide bis(chloroform) crystallizes in the monoclinic space group P21/n with a = 11.683 (8), b = 21.717 (8), c = 20.752 (5) Å, β = 95.03 (5)° and Z = 4 formula units. The crystal structure has been refined to RF = 0.058 for 3894 reflections. The structure consists of two chloroform molecules, octahedrally coordinated complex cations [Ni(phen)3]2+ and nonplanar octaiodide anions I82- each composed of two asymmetric triiodide units I3- weakly associated with an elongated bridging iodine molecule I2.The already known structure of bis(N-methylurotropinium) octaiodide, (UrMe)2I8, has been verified and more accurate crystal data have been collected. The crystal structure has been refined to RF = 0.045 for 1908 reflections. The compound crystallizes in the monoclinic space group P21/c with a = 11.302 (2), b = 9.850 (2), c = 14.188 (2) Å , β = 92.59 (1)° and Z = 2. The anion has the shape of a stretched Z.The structure of bis(N-ethylurotropinium) octaiodide (UrEt)2I8 has been determined and a new configuration (I3-, I5-) for octaiodide ions between Z (I3- · I2 ·I3-) and a “broken” configuration (I3-, I5-) has been observed. The compound crystallizes in the triclinic space group P1̄ with a = 9.741 (3), b = 11.815 (3), c = 15.426 (3) Å, α = 91.80 (2), β = 107.14 (2), γ = 90.04 (2)° and Z = 2. The crystal structure has been refined to RF = 0.037 for 3657 reflections.

Professor Hans Georg von Schnering zum 65. Geburtstag gewidmetInhaltsiibersicht. Die Verbindungen UrPrI, rnit x = 5 und 7 lassen sich durch Umsetzung von N-Propylurotropiniumiodid UrPrI mit uberschussigem Iod I, bei Raumtemperatur aus wal3riger Losung gewinnen. N-Propylurotropiniumpentaiodid C9Ht9N41S kristallisiert in der monoklinen Raumgruppe P 2 , h rnit a = 1007,6(3) pm, b = 1362,5(3) pm, c = 2899,0(9) pm, / 3 = 91,49(3)O und Z = 8. In der Kristallstruktur ordnen sich Kationen UrPr + und Dimere aus stark aufgeweiteten V-formi-gen Anionen Isentlang [0 1 01 zu parallelen Strangen an. N-Propylurotropiniumhept_aiodid C9HI9N4I7 kristallisiert in der triklinen Raumgruppe P I mit a = 970,4(1) pm, b = 971,1(1) pm, c = 1357,8(2) pm, Q! = 106,83(1)O, / 3 = 92,28(1)", y = 105,17(1)" und Z = 2. In der Kristallstruktur wechseln sich Doppelschichten aus Kationen UrPr' und aus vernetzten Anionen 17-langs [00 I] ab. Studies onPolyhalides. 26. On N-Propylurotropinium Polyiodides UrPrI, with x = 5 and 7: Abstract. The salts UrPrI, with x = 5 and 7 are formed by the reaction of N-propylurotropinium iodide UrPrI with excess iodine I, at room temperature from aqueous solution. N-propylurotropinium pentaiodide C9H,9N415 crystallizes monoclinically in P 2 , h with a = 1007.6(3) pm, b = 1362.5(3) pm, dimensional network. c = 2899.0(9) pm, / 3 = 92.49(3)' and Z = 8. The crystal structure is built up from parallel chains of cations UrPr+ and pairs of V-shaped pentaiodide anions Isalong [0 1 01. N-propylurotropinium heptaiodide C9HI9N4I7 crystallizes triclinically in P i with a = 970.4(1) pm, b = 971.1(1) pm, c = 1357.8(2) pm, a = 106.83(1)", /3 = 92.28(1)", y = 105.17(1)0 and Z = 2. The crystal structure is stacked by alternating cationic and anionic double layers along [0 0 I]. The heptaiodide layer shows a two-Einleitung N-Alkylurotropinium-Ionen U r R + (Ur = Urotropin C,H,,N,, R = n-CmHlm+, rnit 1 I m i 6) sind als grol3e niedriggeladene Kationen geeignet, insbesondere auch iodreichere Polyiodid-Ionen 1,"-rnit m/n > 3 in kristal-

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