The salts RTazI(x) with R = Et, i-Pr and t-Bu and 3 less than or equal to x less than or equal to 7 are formed by the reaction of 1,3,5-trialkyl-tetrahy-dro-1,3,5-triazinium iodide RTazI with iodine I-2 from ethanoleous solution. 1,3,5-Triethyl-tetrahydro-1,3,5-triazinium triiodide C9H20N3I3 crystallizes triclinically inwith a = 773.5(1) pm, b = 842.8(1) pm, c = 1370.4(3) pm, alpha = 94.16(1)degrees, beta = 97.34(1)degrees, gamma = 106.35(1)degrees and Z = 2. The crystal structure is stacked by layers of cations EtTaz(+) and of linear symmetric triiodide ions I-3(-) alternating along [0 0 1]. 1,3,5-Tri-iso-propyl-tetrahydro-1,3,5-triazinium triiodide C12H26N3I3 crystallizes triclinically in Pwith a = 822.0(1)pm, b = 832.1(2)pm, c = 1553.6(2)pm, alpha = 78.26(1)degrees, beta = 76.21(1)degrees, gamma = 77.23(1)degrees and Z = 2. The crystal structure is built up from layers of cations i-PrTaz(+) and of linear symmetric triiodide ions I-3(-) alternating along [0 0 1]. 1,3,5-Tri-iso-propyl-tetrahydro-1,3,5-triazinium pentaiodide C12H26N3I5 crystallizes monoclinically in P2(1)/c with a = 1015.4(2) pm, b = 1278.9(1) pm, c = 1811.3(2) pm, beta = 92.47(1)degrees and Z = 4. The cationic (i-PrTaz(+)) and anionic (isolated V-shaped I-5(-)) double layers alternate along [0 0 1]. 1,3,5-Tri-tertiary-butyl-tetrahydro-1,3,5-triazinium iodide C15H32N3I crystallizes monoclinically in P2(1)/n with a = 863.9(1)pm, b = 1655.9(2)pm, c = 1307.6(1) pm, beta = 92.90(1)degrees and Z = 4. Mixed layers built up from cations t-BuTaz(+) and anions I- follow along [0 1 0]. 1,3,5-Tri-tertiary-butyl-tetrahydro-1,3,5-triazinium triiodide C15H32N3I3 crystallizes orthorhombically in Fdd2 with a = 1772.0(4)pm, b = 2477.8(6)pm, c = 2273.4(5)pm and Z = 16. The crystal structure is stacked by mixed layers of cations t-BuTaz(+) and linear symmetric anions I-3(-). 1,3,5-Tri-tertiary-butyl-tetrahydro-1,3,5-triazinium pentaiodide C15H32N3I5 crystallizes monoclinically in C2/m with a = 1219.5(3)pm, b = 1420.9(3) pm, c = 1539.5(3) pm, beta = 94.54(2)degrees and Z = 4. The crystal structure is built up from alternating cationic (t-BuTaz(+)) and anionic (symmetry generated I-5(-)) double layers along [1 0 0]. The triiodide parts of different anionic double layers are linked up by iodine bridges I-2 to ticktack chains. 1,3,5-Tri-tertiary-butyl-tetrahydro-1,3,5-triazinium heptaiodide C15H32N3I7 crystallizes monoclinically in P2(1)/c with a = 1036.0(2)pm, b = 1768.3(4)pm, c = 1699.5(4)pm, beta = 103.11(2)degrees und Z = 4. The crystal structure shows a three-dimensional network made by the alternating linkage of trigonal-pyramidal and Z-shaped heptaiodide ions.

The salts UrRI(3) may be prepared by the reaction of N-alkylurotropinium iodides UrRI with iodine I-2 at room temperature from aqueous solution.N-methylurotropinium triiodide C7H15N4I3 crystallizes monoclinically in P2(1)/c with a = 1300.8(2) pm, b = 1276.0(3) pm, c = 859.3(2) pm, beta = 94.75(2) and Z = 4. The crystal struc ture is built up from layers of cations UrMe(+) and of linear symmetric triiodide ions I-3(-) 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 2 = 4. The cationic (UrEt(+)) and anionic (I-3(-)) layers alternate along [010].N-propylurotropinium triiodide C9H19N4I3 crystallizes monoclinically in P2(1)/c with a = 1885.7(5)pm, b = 1657.1(5)pm, c = 1700.5(4) pm, beta = 112.39(2)degrees and Z = 12. The three independent cations and anions are slightly, but differently distorted.N-butylurotropinium triiodide C10H21N4I3 crystallizes monoclinically in P2(1)/m with a = 991.8(3) pm, b = 757.8(2) pm, c = 1128.2(2) pm, beta = 90.73(2)degrees and Z = 2. The crystal structure is stacked by alternating cationic and anionic layers along [001]. The triiodide ion is asymmetric and linear.

After Raman spectroscopic investigation of the system HgI2/Et(3)SI(x), x = 3, 5, 7, triethylsulfoniumtriiodomer-curatetris(diiodine), (Et(3)S)[Hg2I6](1/2).3I(2) was synthesized by reacting of HgI2 and liquid Et(3)SI(7). The compound crystallizes at room temperature triclinically in the space group P $($) over bar$$ 1 with a = 879.4(7), b = 1209.1(5), c = 1291.5(5) pm, alpha = 96.16(3)degrees, beta = 103.82(6)degrees, gamma = 99.05(5)degrees and Z = 2. The crystal structure is composed of disordered Et(3)S(+) cations, the centrosymmetric complex anion [HgI2/I-2(2)](2-)(2) and three connecting iodine molecules I-2.

The reaction of 1,3,5-trimethyl-hexahydro-1,3,5-triazine (CH3NCH2)(3) with iodine in the molar ratio (CH3NCH2)(3):I-2=2:1 gives the new compound 1,3,5-trimethyl-tetrahydro-1,3,5-triazinium-iodide C6H14N3I. This iodide adds one mole I-2 and forms 1,3,5-trimethyl-tetrahydro-1,3,5-triazinium-triiodide C6H14N3I3. The crystal structure analysis shows a cation, in which two methyl groups and five ring atoms are planar arranged. The third methyl group stands axial to the ring. 1,3,5-Trimethyl-tetrahydro-1,3,5-triazinium-pentaiodide is formed by adding a further mole I-2.

Solid polybromide-containing functional polymers were obtained from basic anion-exchange resins. The chloride or hydroxide anions of the commercial resins were exchanged by bromide, then dried under anaerobic conditions and allowed to react with a gaseous bromine phase. The formation of linear, slightly asymmetric tribromides was proved by Raman and far-IR spectroscopy. The tribromide spectra are characterized by the symmetrical stretching vibration nu-1 at about 160 cm-1 and the antisymmetric stretching vibration nu-3 at about 200 cm-1. If the Br2:Br- molar ratio is greater than 1 an additional band could be observed at about 255 cm-1. This band is assigned to the stretching vibration of coordinated bromine. It is shifted in the direction of free bromine at about 300 cm-1 with increasing bromine content in the functional polymers. According to the spectroscopic results, the anion structure in amorphous polybromide-containing functional polymers can be explained by tribromide ions and bromine molecules interacting with the tribromide. The thermal instability of higher polybromides was also proved spectroscopically.

The structure of molten polyiodides, Et3SI(x)(1)(Et = ethyl; x = 3, 4, 5 and 7), have been investigated by liquid x-ray scattering and Raman spectroscopy techniques at room temperature. The predominant iodine-containing species in Et3SI3(1) is a centrosymmetric I3-ion with a closest I-I distance of 2.915(2) angstrom. The Raman spectra indicate a large bond flexibility of the triiodide ion. The structural results of the iodine-rich melts Et3SI(x)(1), x > 3, are consistent with a three-dimensional network of interconnected I3-ions and I2 molecules. The short-range order bears close similarities to that of pure liquid and solid iodine. The triiodides are on the average solvated by one, two and three iodine molecules for x = 4, 5 and 7, respectively. The coordination mode is flat-on with the I3- and I2 units almost parallel but slightly tilted away from each other like the nearest-neighbour contacts in pure iodine. Previously published conductivity results are consistent with such a structure model.

Mixtures of iodine and dialkylsulphides are liquids with a significant electrical conductivity, especially in the range of high iodine concentrations. A linear relationship exists between the logarithm of the conductivity and the weight percentage of iodine in the mixtures over more than four magnitudes of conductivity and nearly the whole concentration range.

N ‐Alkylurotropinium polyiodides, UrRI x , with different iodine contents and different sizes of alkyl group were investigated by Raman spectroscopy. The spectra were recorded for wavenumber shifts up to 500 cm −1 . It was found that the triiodides, UrRI 3 , contain a symmetrical linear I 3 − ion. The pentaiodides, UrRI 5 , contain no triiodide unit; the anion structure can be described as nearly symmetrical, rectangular L‐shaped I 5 − . An interpretation of the Raman spectra of the heptaiodides, UrRI 7 , is that the anion corresponds to an I 5 − . I 2 structure. This is the first proof of such a heptaiodide. A review of previously published data on the Raman spectra of polyiodides is also given.

ChemInformVolume 19, Issue 15 Isocyclic Compounds ChemInform Abstract: N-Alkylurotropiniumpolyiodides - Preparation and Investigation of the Electrical and Magnetic Properties. H. STEGEMANN, H. STEGEMANN Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorG. JABS, G. JABS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorH. MITTAG, H. MITTAG Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorL. SCHMIDT, L. SCHMIDT Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorH. + FUELLBIER, H. + FUELLBIER Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorP. CIKMACS, P. CIKMACS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorG. PETROVSKIS, G. PETROVSKIS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorA. LUSIS, A. LUSIS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorA. S. ORLIUKAS, A. S. ORLIUKAS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this author H. STEGEMANN, H. STEGEMANN Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorG. JABS, G. JABS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorH. MITTAG, H. MITTAG Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorL. SCHMIDT, L. SCHMIDT Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorH. + FUELLBIER, H. + FUELLBIER Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorP. CIKMACS, P. CIKMACS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorG. PETROVSKIS, G. PETROVSKIS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorA. LUSIS, A. LUSIS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this authorA. S. ORLIUKAS, A. S. ORLIUKAS Sekt. Chem., Ernst-Moritz-Arndt-Univ., DDR-2200 GreifswaldSearch for more papers by this author First published: April 12, 1988 https://doi.org/10.1002/chin.198815147Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume19, Issue15April 12, 1988 RelatedInformation

AbstractMittels einer potentiometrischen Meßanordnung wird die Bildung von N‐Alkylurotropiniumpolyiodiden untersucht. Die Polyiodide werden präpariert, analysiert und ihre elektrischen sowie magnetischen Eigenschaften gemessen. Alle dargestellten Polyiodide sind diamagnetisch. Die magnetische Suszeptibilität ist unabhängig von der magnetischen Feldstärke und der Temperatur. Die elektrische Leitfähigkeit steigt mit dem Iodgehalt. Sie liegt bei Raumtemperatur zwischen 10−11S/cm für die Triiodide und 10−5S/cm für die Heptaiodide. Der Stromtransport wird vorrangig durch Elektronenüberführung im Anionenteilgitter realisiert.