Genistein complexes with amines: structure and properties

(Note: The full text of this document is currently only available in the PDF Version )

Aleksander P. Mazurek, Lech Kozerski, Joanna Sadlej, Robert Kawę, Elżbieta Bednarek, Jerzy Sitkowski, Jan Cz. Dobrowolski, Jan K. Maurin, Krzysztof Biniecki, Janina Witowska, Piotr Fiedor and Jan Pachecka

New amine complexes of genistein in the crystal and the solution state have been studied by X-ray crystallography and by 1H and 13C NMR spectroscopy. The gas-phase structures have been modelled with ab initio quantum chemical calculations. The morpholine–genistein hydrogen bonded complex has been investigated by all the above methods whereas the triethylamine, morpholine and piperazine complexes have been investigated with 1H NOE and 13C NMR spectroscopy. The X-ray results show the genistein–morpholine complex to be formed as a result of proton transfer from the genistein OH group at position C7 to the morpholine nitrogen atom. This complex also has the lowest total energy when compared to other possible complexes. The NMR measurements in solution indicate that the protonated amine is in fast exchange between various interaction sites, the most stable complex being formed at position C7 as in the crystal. The ab initio quantum mechanical calculations show that this position is also the best for interactions. The 13C NMR chemical shifts calculated theoretically are in agreement with experimental values.


  1. G. Capranico, M. Palumbo, S. Tinelli, M. Mabilia, A. Pozzan and F. Zunino, J. Mol. Biol., 1994, 235, 1218 CrossRef CAS.
  2. T. Akiyama, J. Ishida, S. Nakagawa, H. Ogawara, S. Watanabe, N. Itoh, M. Shibuya and Y. Fukami, J. Biol. Chem., 1987, 262, 5592 CAS.
  3. (a) P. S. Fiedor, M. Maksymowicz, K. Biniecki, L. Kozerski, R. Kawęcki, J. Cz. Dobrowolski, J. Pachecka, P. Aranjo, W. Rowiński and A. P. Mazurek, Congress of European Society for Artificial Organs, Warsaw, October 17–19, 1996(Abstract no. 196), p. 3 Search PubMed; (b) A. P. Mazurek, K. Biniecki and L. Kozerski, US Pat. 5, 637 703, 1997, Japan Pat., pending Search PubMed.
  4. F. M. Uckun, W. E. Evans, C. J. Forsyth, K. G. Waddick, L. T. Åhlgren, L. M. Chelström, A. Burkhardt, J. Bolen and D. E. Myers, Science, 1995, 267, 886 CrossRef CAS.
  5. M. Breton, G. Precigoux, Ch. Courseille and M. Hospital, Acta Crystallogr., Sect. B, 1975, 31, 921 CrossRef.
  6. S. Tahara, J. L. Ingham, F. Hanawa and J. Mizutani, Phytochemistry, 1991, 30, 1683 CrossRef CAS.
  7. J.-E. Kinjo, J.-I. Furusawa, J. Baba, T. Takeshita, M. Yamasaki and T. Nohara, Chem. Pharm. Bull., 1987, 35, 4846 CAS.
  8. A. Pelter, R. S. Ward and R. J. Bass, J. Chem. Soc., Perkin Trans. 1, 1978, 666 RSC.
  9. P. C. Yates, J. Mol. Struct. (THEOCHEM), 1991, 231, 201 CrossRef.
  10. R. J. Bass, J. Chem. Soc., Chem. Commun., 1976, 78 RSC.
  11. G. M. Sheldrick, SHELXS86. Program for X-ray structure determination. University of Göttingen, 1986, Germany.
  12. G. M. Sheldrick, SHELXL93. Program for the refinement of crystal structures. University of Göttingen, 1993, Germany.
  13. L. Kozerski, R. Kawęcki, P. Krajewski, P. Gluziński, K. Pupek, P. E. Hansen and M. P. Williamson, J. Org. Chem., 1995, 60, 353 CrossRef.
  14. GAUSSIAN94 (Revision D4). M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales and J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995.
  15. J. A. Pople, R. Seeger and R. Krishnan, Int. J. Quant. Chem. Symp., 1977, 11, 149 Search PubMed.
  16. S. F. Boys and F. Bernardi, Mol. Phys., 1970, 19, 553.
  17. W. Kołos, Theor. Chim. Acta, 1980, 54, 187 CAS.
  18. L. Turi and J. J. Dannenberg, J. Phys. Chem., 1993, 97, 2488 CrossRef CAS.
  19. A. T. Pudzianowski, J. Chem. Phys., 1995, 102, 8029 CrossRef CAS.
  20. K. Wolinski, J. F. Hinton and P. Pulay, J. Am. Chem. Soc., 1990, 112, 8251 CrossRef CAS.
  21. A. E. Hansen and T. D. Bouman, J. Chem. Phys., 1985, 82, 5035 CrossRef CAS.
  22. A. Barszczewicz, M. Jaszuński and L. Stefaniak, Chem. Phys. Lett., 1991, 186, 313 CrossRef CAS.
  23. K. Jackowski, A. Barszczewicz and K. Woźniak, Solid State NMR, 1993, 2, 265 CAS.
  24. M. Pecul, K. Jackowski, K. Woźniak and J. Sadlej, Solid State NMR, 1997, 8, 139 CrossRef CAS.