Crown ether conformations in 1,3-calix[4]arene bis(crown ethers): crystal structures of a caesium complex and solvent adducts and molecular dynamics simulations *

Abstract

The crystal structures of solvent adducts of 1,3-calix[4]arene bis(18-crown-6) 1 and 1,3-calix[4]arene bis(naphtho-18-crown-6) 3 as well as the structure of the caesium complex of 3 have been determined. In 1·3CH₃NO₂ and 3·3CH₃CN the complexed solvent molecules have their methyl group at the centre of the crown ether rings, whereas in 3·C₆H₅CH₃, the solvent is located in the crystal voids. The consequences on the crown ether conformations are noticeable: comparison with previous results shows that the conformation of 1 is only slightly different in its acetonitrile and nitromethane adducts, the conformation with acetonitrile being the same as in the caesium and potassium complexes; the conformation of the acetonitrile adduct of 3 is the same as that in the caesium complex and is strongly different from the one obtained by crystallization in toluene. Molecular dynamics simulations in vacuo were performed on free 3 and on its mononuclear caesium complex, and discussed in terms of the conformational mobility of the crown ether loop.

References

1. Z. Asfari, C. Bressot, J. Vicens, C. Hill, J. F. Dozol, H. Rouquette, S. Eymard, V. Lamare and B. Tournois, Anal. Chem., 1995, 67, 3133.
2. Z. Asfari, S. Wenger and J. Vicens, J. Incl. Phenom., 1994, 19, 137; C. Hill, J. F. Dozol, V. Lamare, H. Rouquette, S. Eymard, B. Tournois, J. Vicens, Z. Asfari, C. Bressot, R. Ungaro and A. Casnati, J. Incl. Phenom., 1994, 19, 399.
3. Z. Asfari, M. Nierlich, P. Thuéry, V. Lamare, J. F. Dozol, M. Leroy and J. Vicens, An. Quím. Int. Ed., 1996, 92, 260.
4. T. J. Haverlock, P. V. Bonnesen, R. A. Sachleben and B. A. Moyer, Radiochim. Acta, 1997, 76, 103.
5. P. Thuéry, M. Nierlich, C. Bressot, V. Lamare, J. F. Dozol, Z. Asfari and J. Vicens, J. Incl. Phenom., 1996, 23, 305.
6. Z. Asfari, C. Naumann, J. Vicens, M. Nierlich, P. Thuéry, C. Bressot, V. Lamare and J. F. Dozol, New J. Chem., 1996, 20, 1183.
7. P. Thuéry, M. Nierlich, V. Lamare, J. F. Dozol, Z. Asfari and J. Vicens, Acta Crystallogr., Sect. C, 1996, 52, 2729.
8. P. Thuéry, M. Nierlich, Z. Asfari and J. Vicens, J. Incl. Phenom., 1997, 27, 169.
9. P. Thuéry, M. Nierlich, V. Lamare, J. F. Dozol, Z. Asfari and J. Vicens, Supramol. Chem., in the press.
10. V. Lamare, C. Bressot, J. F. Dozol, J. Vicens, Z. Asfari, R. Ungaro and A. Casnati, Sep. Sci. Technol., 1997, 32, 175.
11. G. Wipff and M. Lauterbach, Supramol. Chem., 1995, 6, 187.
12. A. Varnek and G. Wipff, J. Mol. Struct. (Theochem), 1996, 363, 67.
13. G. M. Sheldrick, SHELXS 86, Program for the Solution of Crystal Structures, University of Göttingen, 1985.
14. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4; present distributor: Academic Publishers, Dordrecht.
15. MOLEN: An Interactive Structure Solution Procedure, Enraf-Nonius, Delft, 1990.
16. K. Harms, XCAD 4, University of Marburg, 1995.
17. SHELXTL, Version 5/IRIX, Siemens Analytical X-ray Instruments, Madison, WI, 1990.
18. A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, C-34.
19. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
20. D. A. Pearlman, D. A. Case, J. A. Caldwell, W. S. Ross, T. E. Cheatham III, D. M. Ferguson, G. L. Seibel, U. C. Singh, P. Weiner and P. A. Kollman, AMBER 4.1, University of California, San Francisco, 1995.
21. S. J. Weiner, P. A. Kollman, D. T. Nguyen and D. A. Case, J. Comput. Chem., 1986, 7, 230.
22. SYBYL 6.1, Molecular Modeling Software, TRIPOS Inc., 1994.
23. T. J. Marrone, D. S. Hartsough and K. M. Merz, J. Phys. Chem., 1994, 98, 1341.
24. J. Åqvist, J. Phys. Chem., 1990, 94, 8021.
25. P. Guilbaud and G. Wipff, J. Phys. Chem., 1993, 97, 5685.
26. E. Engler and G. Wipff, MDS and MD/DRAW 1.0, Laboratoire de Modélisation et de Simulations Moléculaires (MSM), Université Louis Pasteur, Strasbourg.
27. A. Ikeda, H. Tsuzuki and S. Shinkai, Tetrahedron Lett., 1994, 8417; A. Ikeda and S. Shinkai, J. Am. Chem. Soc., 1994, 116, 3102.
28. P. D. Beer, M. G. B. Drew, P. A. Gale, P. B. Leeson and M. I. Ogden, J. Chem. Soc., Dalton Trans., 1994, 3479.
29. F. Arnaud-Neu, Z. Asfari, B. Souley and J. Vicens, New J. Chem., 1996, 20, 453.
30. T. M. Fyles and R. D. Gandour, J. Incl. Phenom., 1992, 12, 313.
31. Handbook of Chemistry and Physics, ed. D. R. Lide, CRC Press, Boca Raton, FL, 72nd edn., 1992, pp. 15–43.
32. R. Ungaro, A. Casnati, F. Ugozzoli, A. Pochini, J. F. Dozol, C. Hill and H. Rouquette, Angew. Chem., Int. Ed. Engl., 1994, 33, 1506.
33. J. A. A. de Boer, D. N. Reinhoudt, S. Harkema, G. J. van Hummel and F. de Jong, J. Am. Chem. Soc., 1982, 104, 4073.
34. J. H. Burns, J. C. Bryan, M. C. Davis and R. A. Sachleben, J. Incl. Phenom., 1996, 26, 197.
35. P. Thuéry, M. Nierlich, Z. Asfari and J. Vicens, unpublished work.
36. See, for example: (a) B. L. Allwood, S. E. Fuller, P. C. Y. K. Ning, A. M. Z. Slawin, J. F. Stoddart and D. J. Williams, J. Chem. Soc., Chem. Commun., 1984, 1356; (b) R. D. Rogers, P. D. Richards and E. J. Voss, J. Incl. Phenom., 1988, 6, 65; (c) R. L. Garrell, J. C. Smyth, F. R. Fronczec and R. D. Gandour, J. Incl. Phenom., 1988, 6, 73; (d) R. D. Rogers, J. Incl. Phenom., 1988, 6, 629; (e) F. Weller, H. Borgholte, H. Stenger, S. Vogler and K. Dehnicke, Z. Naturforsch., Teil B, 1989, 44, 1524; (f) K. Panneerselvam, K. K. Chacko, E. Weber and H. J. Köhler, J. Incl. Phenom., 1990, 9, 337; (g) M. R. Caira and R. Mohamed, Acta Crystallogr., Sect. B, 1993, 49, 760; (h) F. Vögtle, W. M. Müller and W. H. Watson, Top. Curr. Chem., 1984, 125, 131.
37. J. H. Burns, personal communication.
38. D. J. Cram, Angew. Chem., Int. Ed. Engl., 1988, 27, 1009.
39. G. Ranghino, S. Romano, J. M. Lehn and G. Wipff, J. Am. Chem. Soc., 1985, 107, 7873.
40. L. Troxler and G. Wipff, J. Am. Chem. Soc., 1994, 116, 1468.
41. G. Wipff and L. Troxler, in Computational Approaches in Supramolecular Chemistry, ed. G. Wipff, Kluwer, Dordrecht, 1994, p. 319.
42. A. Varnek and G. Wipff, J. Phys. Chem., 1993, 97, 10 840.
43. P. Guilbaud, A. Varnek and G. Wipff, J. Am. Chem. Soc., 1993, 115, 8298.
44. A. F. Danil de Namor, N. Apaza de Sueros, M. A. McKervey, G. Barrett, F. Arnaud Neu and M. J. Schwing-Weill, J. Chem. Soc., Chem. Commun., 1991, 1546.