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Hyperfine Interactions

, Volume 181, Issue 1–3, pp 59–68 | Cite as

Anomalous H/D isotope effect on 35Cl NQR frequencies in piperidinium p-chlorobenzoate

  • Ryo Nakano
  • Hisashi HondaEmail author
  • Taiki Kimura
  • Eiichi Nakata
  • Satoshi Takamizawa
  • Sumiko Noro
  • Shin’ichi Ishimaru
Article

Abstract

Anomalous isotope effects were detected in the 35Cl nuclear quadrupole resonance (NQR) frequency of piperidinium p-chlrobenzoate (C5H10NH· ClC6H4COOH) by deuteration of hydrogen atoms. The atoms were determined to form two kinds of N–H···O type H-bonds in the crystal structure. Large frequency shifts of the 35Cl resonance lines reaching 288 kHz at 77 K and 278 kHz at room temperature were caused upon deuteration, in spite of the fact that the Cl atoms in the molecule do not form hydrogen bonds in the crystal. Results of single crystal X-ray diffraction measurements and density-functional-theorem calculations suggest that a dihedral-angle change of 1.8° between benzene and the piperidine ring contributes to 35Cl NQR anomalous frequency shifts.

Keywords

Anomalous H/D isotope effect 35Cl NQR frequency 

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References

  1. 1.
    Blinc, R., Mali, M., Trontelj, Z.: Chlorine-35 and chlorine-37 quadrupole resonance in normal and deuterated potassium hydrogen and ammonium hydrogen trichloroacetates. Phys. Lett., A 25(4), 289–290 (1967)CrossRefADSGoogle Scholar
  2. 2.
    Pies, W., Weiss, A.: Chlorine-35 nuclear quadrupole resonance in chlorophenols, ClxC6H5 − xOH, and deuterated 2,4,6-trichlorophenol, 2,4,6-Cl3C6H2OD. Substituent effect of the hydroxyl group and hydrogen-deuterium isotope effect. Adv. Nucl. Quadrup. Reson. 7, 57–70 (1974)Google Scholar
  3. 3.
    Lynch, R.J., Waddington, T.C., O’Shea, T.A., Smith, J.A.S.: Investigation of the hydrogen bonding in chlorocarboxylate anions using 35Cl quadrupole resonance spectroscopy. J. Chem. Soc., Faraday Trans. 2 72(11), 1980–1990 (1976)CrossRefGoogle Scholar
  4. 4.
    Borchers, D., Weiss, A.: Structure, hydrogen bonds and phase transition in ethylenediammonium hexachlorometallates, [H3N(CH2)2NH3]2 + [XCl6]2 − , X = tin, lead, tellurium,and platinum A chloline-35 x-ray diffraction study. Ber. Bunsen-Ges. 90(8), 718–725 (1986)Google Scholar
  5. 5.
    Shirley, W.M.: Nuclear quadrupole resonance studies of hydrogen bonding in trans-dichlorobis(ethylenediamine)cobalt(III) diaquahydrogen chloride. Spectrochim. Acta, Part A 43A(4), 565–568 (1987)CrossRefGoogle Scholar
  6. 6.
    Sasane, A., Shinohara, H., Mori, Y., Kume, Y., Asaji, T., Nakamura, D.: A temperature dependence study of chlorine-35 nuclear quadrupole resonance frequencies in some hexachloroplatinate(IV) hexahydrates. Z. Naturforsch. A 42(6), 611–616 (1987)Google Scholar
  7. 7.
    Mackowiak, M., Koziol, P.: Effect of pressure on the symmetric hydrogen bond in potassium hydrogen bis(trichloroacetate). Phys. Status Solidi, A Appl. Res. 108(2), 739–745 (1988)CrossRefGoogle Scholar
  8. 8.
    Kalenik, J., Majerz, I., Malarski, Z., Sobczyk, L.: Infrared and chlorine-35 nuclear quadrupole resonance studies of hydrogen-bonded adducts of 2-chlorobenzoic acid derivatives. Chem. Phys. Lett. 165(1), 15–18 (1990)CrossRefADSGoogle Scholar
  9. 9.
    Horiuchi, K.: Temperature dependence of the effect of deuteration on the chlorine-35 quadrupole resonance frequency in an hexaaquamagnesium(2+) hexachlorostannate(IV) crystal. J. Chem. Soc., Faraday Trans. 89(18), 3359–3362 (1993)CrossRefGoogle Scholar
  10. 10.
    Zdanowska-Fraczek, M.: 35Cl NQR study of geometric isotope effects in hydrogen-bonded chloroacetic acid salts. J. Mol. Struct. 321(1–2), 53–56 (1994)CrossRefADSGoogle Scholar
  11. 11.
    Zdanowska-Fraczek, M.: NQR studies of charge distribution in hydrogen-bonded chloroacetates. Ber. Bunsen-Ges. 102(3), 340–343 (1998)Google Scholar
  12. 12.
    Honda, H.: Even–odd effect of 35Cl quadrupole coupling constants in solid n-alkylammonium chlorides (C5–C10). Z. Naturforsch. A 58(11), 623–630 (2003)Google Scholar
  13. 13.
    Kashino, S., Sumida, Y., Haisa, M.: Crystal and molecular structures of the 1:1 addition compounds of piperidine with p-bromobenzoic acid and p-chlorobenzoic acid. Acta Crystallogr., B 29, 1374 (1972)Google Scholar
  14. 14.
    Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Jr., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C., Pople, J.A.: Gaussian 03, Revision B.04, Gaussian, Inc., Pittsburgh PA (2003)Google Scholar
  15. 15.
    Bayer, H.: Zur Theorie der spin-gitterrelaxation in molekulkristallen. Z. Physik 130, 227–238 (1951)CrossRefADSGoogle Scholar
  16. 16.
    Kushida, T.: The influence of lattice vibration on the pure quadrupole line. J. Sci. Hiroshima Univ., Ser. A 19, 327–365 (1955)Google Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • Ryo Nakano
    • 1
  • Hisashi Honda
    • 1
    • 2
    Email author
  • Taiki Kimura
    • 2
  • Eiichi Nakata
    • 1
  • Satoshi Takamizawa
    • 1
    • 2
  • Sumiko Noro
    • 1
    • 2
  • Shin’ichi Ishimaru
    • 3
  1. 1.Graduate School of Integrated ScienceYokohama City UniversityYokohamaJapan
  2. 2.Faculty of ScienceYokohama City UniversityYokohamaJapan
  3. 3.Department of Green and Sustainable ChemistryTokyo Denki UniversityTokyoJapan

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