Biomimetic control of iron oxide and hydroxide phases in the iron oxalate system *

Abstract

The syntheses of mineral phases of iron formed under hydrolytic conditions have been studied using ambient and hydrothermal methods in the presence and absence of the oxalate (ox) template. A systematic survey of experimental parameters revealed how the oxolate template can influence crystal morphology, iron oxidation state and the nature of the phase formed. In addition to observing biomimetic control over crystal morphology of magnetite, two iron(II) hydrolytic oxalate phases were observed, humboldtine, Fe^II(ox)(H₂O)₂, and the new phase, Fe^II₂(ox)(OH)₂, which was identified by single-crystal X-ray diffraction.

References

1. S. Mann, J. Chem. Soc., Dalton Trans., 1997, 3953.
2. G. A. Ozin, J. Chem. Soc., Dalton Trans., 1997, 3941.
3. S. Mann and G. A. Ozin, Nature (London), 1996, 382, 313.
4. B. R. Heywood and S. Mann, Chem. Mater., 1994, 6, 311.
5. D. Walsh and S. Mann, Nature (London), 1995, 377, 320.
6. D. Walsh and S. Mann, Chem. Mater., 1996, 8, 1944.
7. R. B. Frankel, Iron Biominerals, eds. R. B. Frankel and R. P. Blakemore, Plenum, New York, 1990, p. 1.
8. S. L. Heath and A. K. Powell, Angew. Chem., Int. Ed. Engl., 1992, 31, 191.
9. A. K. Powell, S. L. Heath, D. Gatteschi, L. Pardi, R. Sessoli, G. Spina, F. Del Giallo and F. Pieralli, J. Am. Chem. Soc., 1995, 117, 2491.
10. S. L. Heath and A. K. Powell, Comments Inorg. Chem., 1994, 15, 255.
11. C. J. Harding, R. K. Henderson and A. K. Powell, Angew. Chem., Int. Ed. Engl., 1993, 32, 570.
12. S. O. H. Gutschke, M. Molinier, A. K. Powell, R. E. P. Winpenny and P. T. Wood, Chem. Commun., 1996, 823.
13. S. O. H. Gutschke, M. Molinier, A. K. Powell and P. T. Wood, Angew. Chem., Int. Ed. Engl., 1997, 36, 991.
14. TEXSAN Structure Analysis Software, Molecular Structure Corporation, Houston, TX, 1992.
15. G. M. Sheldrick, SHELXTL PLUS, Siemens Analytical X-Ray Instruments, Madison, WI, 1990.
16. G. M. Sheldrick, SHELXL 93, Program for Crystal Structure Refinement, University of Göttingen, 1993.
17. J. Hugget, Liebigs. Ann. Chem., 1929, 10, 445.
18. T. Kanzaki and T. Katsura, J. Chem. Soc., Dalton Trans., 1986, 1243.
19. F. Mazzi and C. Garavelli, Period. Mineral., 1957, 26, 269.
20. R. Deyrieux and A. Peneloux, Bull. Soc. Chim. Fr., 1969, 8, 2675.
21. T. Adschiri, K. Kanazawa and K. Arai, J. Am. Ceram. Soc., 1992, 75, 1019.
22. T. Dubois and G. Demazeau, Mater. Lett., 1994, 19, 38.
23. P. O'Neill, Environmental Chemistry, Chapman and Hall, London, 2nd edn., 1993.
24. K. B. Krauskopf and D. K. Bird, Introduction to Geochemistry, McGraw-Hill, New York, 3rd edn., 1995.
25. R. M. Garrels and L. Christ, Solutions, Minerals and Equilibria, Harper and Row, New York, 1965.
26. H. A. Lowenstamm, Bull. Geol. Soc. Am., 1962, 13, 435.
27. A. Rabenau, Angew. Chem., Int. Ed. Engl., 1985, 24, 1026.
28. C. M. Flynn, Chem. Rev., 1984, 84, 31.
29. W. Schneider and B. Schwynn, Aquatic Surface Chemistry, ed. W. Stumm, Wiley, New York, 1987, p. 167.
30. A. F. Wells, Structural Inorganic Chemistry, Oxford University Press, London, 3rd edn., 1962.
31. S. L. Heath, P. A. Jordan, I. D. Johnson, G. R. Moore, A. K. Powell and M. Helliwell, J. Inorg. Biochem., 1995, 59, 785.
32. P. Ramdohr and H. Strunz, Klockmann's Lehrbuch der Mineralogie, Ferdinand Enke Verlag, Stuttgart, 1967p. 757.
33. Yu. D. Kondrashov, V. S. Bogdanov, S. N. Golubev and G. F. Pron, Zh. Strukt. Khim., 1985, 26, 90.
34. S. Mann and R. B. Frankel, Biomineralization. Chemical and Biological Perspectives., eds. S. Mann, J. Webb and R. J. P. Williams, VCH, Weinheim, 1989, p. 389.