Metal iodides in polyiodide networks. The structural chemistry of CdI2 with an excess of iodine[hair space]*

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

Per H. Svensson, Lars Bengtsson-Kloo and Per Persson


Abstract

The reaction between [Me3S][I5] and CdI2 at 80 °C resulted in the compound [Me3S][Cd2I6]1/2·3I2, which has been characterised by X-ray diffraction, Raman spectroscopy and EXAFS. The structure consists of layers of I2-bridged, dimeric Cd2I62– units interspaced with interacting I2 molecules arranged almost perpendicularly to the cadmium-containing layers. The Cd2I62– units consist of edge-sharing CdI4 tetrahedra. The I2 molecules have intramolecular distances ranging from 2.73 to 2.74 Å and intermolecular distances ranging from 3.37 to 3.56 Å. The I2-bridged Cd2I62– dimers create a network that can be described as infinite chains of I2 co-ordinated in a zigzag manner to the Cd2I62– dimers, interspaced by formal I10 units. The Raman spectrum is dominated by a peak at about 185 cm–1, which confirms the charge-transfer interaction of I2 with the Cd2I62– units. The EXAFS of Cd (K shell) was determined for a 1∶10 mixture of CdI2–[Et3S][I7] confirming the structural relationship of CdII in the liquid reaction medium and the isolated polyiodide compound. For comparison, the crystal structures of iodine-free [Et3S][Cd2I6]1/2 and two phases of polymeric [Me3S][CdI3] were also determined.


References

  1. P. Coppens, in Extended Linear Chain Compounds, ed. J. S. Miller, Plenum, New York, 1982, vol. 1, p. 333 Search PubMed.
  2. T. J. Marks and D. W. Kalina, in Extended Linear Chain Compounds, ed. J. S. Miller, Plenum, New York, 1982, vol. 1, p. 197 Search PubMed.
  3. K.-F. Tebbe, in Homoatomic Rings, Chains and Macromolecules of Main-Group Elements, ed. A. L. Rheingold, Elsevier, Amsterdam, 1977, p. 551 Search PubMed.
  4. P. H. Svensson and L. Bengtsson-Kloo, in preparation.
  5. B. K. Teo, EXAFS: Basic Principles and Data Analysis, Inorganic Chemistry Concepts, vol. 9, Springer, Berlin, 1986 Search PubMed.
  6. A. L. Ankudinov, Ph.D. Thesis, University of Washington, 1996.
  7. T. Ressler, WINXAS, J. Phys., 1997, 7, 269 Search PubMed.
  8. N. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, 39, 158 CrossRef.
  9. A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 1968, 24, 351 CrossRef.
  10. A. Altomare, M. C. Burla, M. Camalli, M. Cascarano, C. Giacovazzo, A. Guagliardi and G. Polidori, J. Appl. Crystallogr., 1994, 27, 435 CrossRef.
  11. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, Houston, TX, 1985, 1992.
  12. F. van Bolhuis, P. B. Koster and T. Migchelsen, Acta Crystallogr., 1967, 23, 90 CrossRef CAS.
  13. I. L. Karle, J. Chem. Phys., 1955, 23, 1739 CAS.
  14. D. D. DesMarteau, T. Grelbig, S.-H. Wang and K. Seppelt, Angew. Chem., Int. Ed. Engl., 1990, 29, 1448 CrossRef.
  15. T. Drews, R. Marx and K. Seppelt, Chem. Eur. J., 1996, 2, 1303 CrossRef CAS.
  16. E. Ruiz and S. Alvarez, J. Am. Chem. Soc., 1995, 117, 2877 CrossRef CAS.
  17. L. Bengtsson, H. Füllbier, B. Holmberg and H. Stegemann, Mol. Phys., 1991, 73, 283 CAS.
  18. P. L. Goggin, R. J. Goodfellow and K. Kessler, J. Chem. Soc., Dalton Trans., 1977, 1914 RSC.
  19. H. Stegemann, K.-F. Tebbe and L. A. Bengtsson, Z. Anorg. Allg. Chem., 1995, 621, 165 CrossRef CAS.
  20. E. S. Lang and J. Strähle, Z. Anorg. Allg. Chem., 1996, 622, 981 CrossRef.
  21. E. Dubler and L. Linowsky, Helv. Chim. Acta, 1975, 58, 2604 CrossRef CAS.
  22. K.-F. Tebbe, Z. Anorg. Allg. Chem., 1982, 489, 93 CrossRef CAS.
  23. K.-F. Tebbe and M. Plewa, Z. Anorg. Allg. Chem., 1982, 489, 111 CrossRef CAS.
  24. M. J. Almond, M. G. B. Drew, D. A. Rice, G. Salisbury and M. J. Taylor, J. Organomet. Chem., 1996, 522, 265 CrossRef CAS.
  25. C. Bellitto, M. Bonamico, G. Dessy, V. Fares and A. Flamini, J. Chem. Soc., Dalton Trans., 1986, 595 RSC.
  26. L. A. Bengtsson, B. Noren and H. Stegemann, Acta Chem. Scand., 1995, 49, 391 CAS.
Click here to see how this site uses Cookies. View our privacy policy here.