Complexation-mediated crystallization. Crystallization of sodium acetate trihydrate needles from cyclohexane solution

  • Kenneth M. Doxsee
  • Raymond C. Stevens


The phenomenon of complexation-mediated crystallization is introduced and proposed as a new means for the preparation of novel forms of materials. Attempted crystallization of complexes of salts with crown ethers often results in the precipitation of the uncomplexed salt rather than the complex. In this study, a solution of the 15-crown-5 complex of sodium acetate in cyclohexane precipitated uncomplexed sodium acetate trihydrate as single crystals. The crystal morphology (long needles) of this crystalline sodium acetate stands in sharp contrast to the hexagonal plates known to form from aqueous solution. X-ray diffraction analysis revealed that sodium acetate as crystallized from cyclohexane ‘solution’ adopted a crystal lattice identical to that in sodium acetate crystallized from aqueous solution. Possible origins of the change in crystal morphology are discussed.

Key words

Sodium acetate crystallization non-aqueous morphology 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Notes and References

  1. 1.
    Work carried out at the Department of Chemistry, University of Southern California, Los Angeles, California.Google Scholar
  2. 2.
    See, e.g., D. J. Cram and K. N. Trueblood: inTopics in Current Chemistry, Vol. 98, pp. 43–106. Springer-Verlag: New York (1981).Google Scholar
  3. 3.
    This phenomenon was perhaps first discussed by Pedersen in his earliest reports of crown ether synthesis: C. J. Pedersen:J. Am. Chem. Soc. 89, 7017 (1967).Google Scholar
  4. 4.
    V. M. Padmanabhan:Curr. Sci. (India)21, 97 (1952).Google Scholar
  5. 5.
    A. Kalman:Acta Crystallogr. 19, 853 (1965).Google Scholar
  6. 6.
    T. S. Cameron, Kh. M. Mannan, and Md. O. Rahman:Acta Crystallogr., Sect. B 32, 87 (1976).Google Scholar
  7. 7.
    K. -T. Wei and D. L. Ward:Acta Crystallogr., Sect. B 33, 522 (1977).Google Scholar
  8. 8.
    L. Y. Hsu and C. E. Nordman:Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 39, 690 (1983).Google Scholar
  9. 9.
    V. A. Efremov, N. O. Endeladze, V. M. Agre, and V. K. Trunov:Zh. Struct. Khim. 27, 177 (1986) [(J. Struct. Chem. 27, 498 (1986)].Google Scholar
  10. 10.
    N. Zelingher, J. Flicstein, and A. Zangvil:J. Crystal Growt 42, 253 (1977).Google Scholar
  11. 11.
    Sheldrick, G. M. SHELX System of Crystallographic Programs; Cambridge University: Cambridge, England (1986).Google Scholar
  12. 12.
    Sheldrick, G. M. SHELX System of Crystallographic Programs; Cambridge University: Cambridge, England (1976).Google Scholar
  13. 13.
    See Ref. 4–9 (aqueous) and 17 (aqueous acetic acid). Formamide work: A. G. Kovaleva:Russ. J. Inorg. Chem. 29, 371 (1984).Google Scholar
  14. 14.
    See, for example, J. W. Mullin: inCrystal Growth (Ed. B. R. Pamplin), pp. 289–325. Pergamon Press: New York (1975).Google Scholar
  15. 15.
    C. Oldham: inComprehensive Coordination Chemistry (Ed. G. Wilkinson, Vol. 2), pp. 435–459. Pergamon Press: New York (1987).Google Scholar
  16. 16.
    P. Groth:Chem. Krist., Vol. III, p. 64. Engelmann: Leipzig (1909).Google Scholar
  17. 17.
    J. C. Speakman and H. H. Mills:J. Chem. Soc. 1164 (1961).Google Scholar
  18. 18.
    For representative examples and reviews, see: L. Addadi, Z. Berkovitch-Yellin, I. Weissbuch, M. Lahav, and L. Leiserowitz:Top. Stereochem. 16, 1 (1986); L. Addadi, M. Cohen, M. Lahav, and L. Leiserowitz:J. Chim. Phys. 83, 831 (1986); L. Addadi, Z. Berkovitch-Yellin, I. Weissbuch, J. van Mil, L. J. W. Shimon, M. Lahav, and L. Leiserovitz:Angew. Chem. Int. Ed. Engl. 24, 466 (1985); L. Addadi, Z. Berkovitch-Yellin, N. Domb, E. Gati, M. Lahav, and L. Leiserowitz:Nature 296, 21 (1982).Google Scholar
  19. 19.
    A detailed understanding of such crown ether interactions may well prove extremely elusive, with any explanations really needing to go to the very heart of the nature of the complexation/decomplexation process.Google Scholar
  20. 20.
    See, for example: J. W. Mullin:Crystallization, 2nd edition. Butterworth: London (1972).Google Scholar
  21. 21.
    This of course represents an extreme simplification; sodium acetate ionic structures in aqueous solution most likely differ significantly from those of the complex in cyclohexane solution. Nevertheless, this discussion serves to suggest some of the possible factors entering into the alteration of crystal habit under the conditions of complexation-mediated crystallization.Google Scholar
  22. 22.
    Photographs of the needles obtained from cyclohexane solution were unfortunately not obtained. However, we have discovered that sodium acetate trihydrate trihydrate may be recrystallized from isopropanol in the form of needles of identical appearance. The photograph in Figure 1 is of these needles. Importantly, the discussion of selective solvation presented in the text appears completely consistent with needle formation from isopropanol.Google Scholar

Copyright information

© Kluwer Academic Publishers 1990

Authors and Affiliations

  • Kenneth M. Doxsee
    • 1
  • Raymond C. Stevens
    • 1
  1. 1.Department of ChemistryUniversity of OregonEugeneUSA

Personalised recommendations