Complexation of a hexameric uranium(VI) cluster by p-benzylcalix[7]arene

Abstract

The reaction of uranyl nitrate hexahydrate with p-benzylcalix[7]arene (H₇L) in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulted in the formation of the compound (UO₂²⁺)₆(L^7–)₂(O^2–)₂(HDABCO⁺)₆·3CH₃CN· CHCl₃·5CH₃OH·3H₂O 1, whose crystal structure has been determined. In the symmetry-centred complex core a hexanuclear uranium(VI) cluster is surrounded by two calixarene units. Each calixarene, in a conformation different from the usual one, encompasses two UO₂²⁺ moieties, which are bonded to three or four phenolic oxygen atoms and also one to the other by one of their oxygen atoms. The two other UO₂²⁺ ions are located between the two calixarene moieties and are involved, together with one of the former ions, in two pseudo-trigonal µ₃-oxo-centred assemblies. This complex, which represents one of the largest metal ion assemblies in calixarene chemistry, illustrates the ‘cluster keeper’ character of the larger calixarenes.

References

1. S. Shinkai, H. Koreishi, K. Ueda, T. Arimura and O. Manabe, J. Am. Chem. Soc., 1987, 109, 6371.
2. J. M. Harroweld, M. I. Ogden and A. H. White, J. Chem. Soc., Dalton Trans., 1991, 979.
3. J. M. Harroweld, M. I. Ogden and A. H. White, J. Chem. Soc., Dalton Trans., 1991, 2625.
4. P. Thuéry, N. Keller, M. Lance, J. D. Vigner and M. Nierlich, Acta Crystallogr., Sect. C, 1995, 51, 1570; New. J. Chem., 1995, 19, 619.
5. P. Thuéry, M. Lance and M. Nierlich, Supramol. Chem., 1996, 7, 183.
6. P. Thuéry and M. Nierlich, J. Inclusion. Phenom., 1997, 27, 13.
7. P. Thuéry, M. Nierlich, M. I. Ogden and J. M. Harroweld, Supramol. Chem., 1998, 9, 297.
8. P. D. Beer, M. G. B. Drew, D. Hesek, M. Kan, G. Nicholson, P. Schmitt, P. D. Sheen and G. Williams, J. Chem. Soc., Dalton Trans., 1998, 2783.
9. P. C. Leverd, P. Berthault, M. Lance and M. Nierlich, Eur. J. Inorg. Chem., 1998, 1859.
10. J. Harroweld, Gazz. Chim. Ital., 1997, 127, 663.
11. X. Delaigue, J. M. Harroweld, M. I. Ogden and A. H. White, manuscript in preparation.
12. M. I. Ogden and J. M. Harroweld, unpublished result.
13. C. D. Gutsche, D. F. Stewart, J. M. Harroweld and M. I. Ogden, to be published.
14. P. Thuéry and M. Nierlich, J. Chem. Soc., Dalton Trans., 1997, 1481.
15. B. Souley, Z. Asfari and J. Vicens, Pol. J. Chem., 1992, 66, 959.
16. Kappa-CCD Software, Nonius B. V., Delft, 1998.
17. Z. Otwinowski and W. Minor, Methods Enzymol., 1997, 276, 307.
18. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
19. G. M. Sheldrick, SHELXL 93, Program for the Renement of Crystal Structures, University of Göttingen, 1993.
20. A. L. Spek, PLATON, University of Utrecht, 1998.
21. G. M. Sheldrick, SHELXTL, University of Göttingen, (distributed by Bruker AXS, Madison, WI) 1997.
22. M. Åberg, Acta Chem. Scand., Sect. A, 1976, 30, 507.
23. A. Perrin and J. Y. Le Marouille, Acta Crystallogr., Sect. B, 1977, 33, 2477.
24. A. Perrin, J. Inorg. Nucl. Chem., 1977, 39, 1169.
25. A. J. Zozulin, D. C. Moody and R. R. Ryan, Inorg. Chem., 1982, 21, 3083.
26. G. Van den Bossche, M. R. Spirlet, J. Rebizant and J. Goart, Acta Crystallogr., Sect. C, 1987, 43, 837.
27. U. Turpeinen, R. Hämäläinen, I. Mutikainen and O. Orama, Acta Crystallogr., Sect. C, 1996, 52, 1169.
28. R. L. Lintvedt, M. J. Heeg, N. Ahmad and M. D. Glick, Inorg. Chem., 1982, 21, 2350.
29. P. Charpin, M. Lance, M. Nierlich, D. Vigner, J. Livet and C. Musikas, Acta Crystallogr., Sect. C, 1986, 42, 1691.
30. T. J. Hall, C. J. Mertz, S. M. Bachrach, W. G. Hipple and R. D. Rogers, J. Cryst. Spectrosc. Res., 1989, 19, 499.
31. S. Siegel, A. Viste, H. R. Hoekstra and B. Tani, Acta Crystallogr., Sect. B, 1972, 28, 117.
32. J. C. Taylor, A. Ekstrom and C. H. Randall, Inorg. Chem., 1978, 17, 3285.
33. D. Rose, Y. D. Chang, Q. Chen and J. Zubieta, Inorg. Chem., 1994, 33, 5167.
34. T. S. Franczyk, K. R. Czerwinski and K. N. Raymond, J. Am. Chem. Soc., 1992, 114, 8138.
35. D. M. Barnhart, C. J. Burns, N. N. Sauer and J. G. Watkin, Inorg. Chem., 1995, 34, 4079.
36. R. G. Denning, in Gmelin Handbook of Inorganic Chemistry, Uranium, Supplement Vol. A6, 8th edn, Springer, Berlin, 1983, p. 31.
37. P. Pyykkö, L. J. Laakkonen and K. Tatsumi, Inorg. Chem., 1989, 28, 1801.
38. M. Perrin, S. Lecocq and Z. Asfari, C. R. Acad. Sci. Paris, 1990, 310, 515.
39. G. D. Andreetti, F. Ugozzoli, Y. Nakamoto and S. I. Ishida, J. Inclusion Phenom., 1991, 10, 241.
40. F. Ugozzoli and G. D. Andreetti, J. Inclusion Phenom., 1992, 13, 337.
41. P. Thuéry and M. Nierlich, unpublished results.