Reaction of thiones with dihalogens; comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione–diiodine, –dibromine and –iodine monobromide

Abstract

Reaction of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione 1 with diiodine or iodine monobromide in CH₂Cl₂ resulted in the formation of molecular charge-transfer complexes 1·I₂ and 1·IBr respectively. Both complexes have been characterised crystallographically and contain a linear S–I–X (X = I or Br) moiety with the sulfur adopting a tetrahedral geometry taking into account the stereochemically active lone pairs. The S–I [2.716(3)] and I–I [2.808(3) Å] bond lengths in 1·I₂ are similar to those reported for diiodine complexes of related thione donors. The adduct 1·IBr is the first crystallographically characterised thione–iodine monobromide charge-transfer complex. The S–I distance [2.589(2) Å] is shorter than that in 1·I₂, consistent with IBr being a stronger acceptor than I₂. The I–Br distance [2.7138(11) Å] is lengthened with respect to that in unco-ordinated IBr, but within bonding distance when compared to the sum of the van der Waals radii for iodine and bromine (3.75 Å). Treatment of 1 with dibromine under identical conditions resulted in the formation of the adduct 1·Br₂ and the dithiolylium salt [C₅H₆S₄Br][Br₃]·½Br₂ 2. Treatment of 1 with Br₂ in toluene led to the isolation of 1·Br₂ only. The crystal structure of 1·Br₂ shows the compound to contain a linear Br–S–Br moiety with the sulfur in a T-shaped or Ψ-trigonal bipyramidal environment (taking into account the stereochemically active lone pairs). The structure of 2 reveals a three component system consisting of the [C₅H₆S₄Br]⁺ cation, the [Br₃]^– anion and a molecule of Br₂ in a 2∶2∶1 ratio. These components are held in the lattice by a series of weak intermolecular interactions which link the tribromide ions and dibromine molecules into zigzag chains.

References

1. S. M. Godfrey, C. A. McAulie, R. G. Pritchard and J. M. Sheffeld, Chem. Commun., 1998, 921; S. M. Godfrey, C. A. McAulie, I. Mushtaq, R. G. Pritchard and J. M. Sheffeld, J. Chem. Soc., Dalton Trans., 1998, 3815; N. Bricklebank, S. M. Godfrey, H. P. Lane, C. A. McAulie, R. G. Pritchard and J. M. Moreno, J. Chem. Soc., Dalton Trans., 1995, 3873; N. Bricklebank, S. M. Godfrey, H. P. Lane, C. A. McAulie and R. G. Pritchard, J. Chem. Soc., Dalton Trans., 1995, 1759; N. Bricklebank, S. M. Godfrey, H. P. Lane, C. A. McAuliffe, R. G. Pritchard and J. M. Moreno, J. Chem. Soc., Dalton Trans., 1994, 2421.
2. F. Ruthe, W. W. du Mont and P. G. Jones, Chem. Commun., 1997, 1947; R. D. Bailey, G. W. Drake, M. Grabarczyk, T. W. Hanks, L. L. Hook and W. T. Pennington, J. Chem. Soc., Perkin Trans. 2, 1997, 2773.
3. (a) D. C. Apperley, N. Bricklebank, S. L. Burns, D. E. Hibbs, M. B. Hursthouse and K. M. A. Malik, J. Chem. Soc., Dalton Trans., 1998, 1289; (b) S. M. Godfrey, S. L. Jackson, C. A. McAulie and R. G. Pritchard, J. Chem. Soc., Dalton Trans., 1997, 4499; (c) A. J. Blake, F. A. Devillanova, A. Garau, L. M. Gilby, R. O. Gould, F. Isaia, V. Lippolis, S. Parsons, C. Radek and M. Schroder, J. Chem. Soc., Dalton Trans., 1998, 2037; (d) A. J. Blake, F. Cristiani, F. A. Devillanova, A. Garau, L. M. Gilby, R. O. Gould, F. Isaia, V. Lippolis, S. Parsons, C. Radek and M. Schroder, J. Chem. Soc., Dalton Trans., 1997, 1337; (e) F. Cristiani, F. Delmartin, F. A. Devillanova, F. Isaia, V. Lippolis and G. Verani, Inorg. Chem., 1994, 33, 6315.
4. M. D. Rudd, S. V. Lindeman and S. Husebye, Acta Chem. Scand., 1997, 51, 689.
5. (a) F. Bigoli, P. Deplano, M. L. Mercuri, M. A. Pellinghelli, A. Sabatini, E. F. Trogu and A. Vacca, J. Chem. Soc., Dalton Trans., 1996, 3583; (b) D. Atzei, P. Deplano, E. F. Trogu, F. Bigoli, M. A. Pellinghelli, A. Sabatini and A. Vacca, Can. J. Chem., 1989, 67, 1416; (c) D. Atzei, P. Deplano, E. F. Trogu, F. Bigoli, M. A. Pellinghelli and A. Vacca, Can. J. Chem., 1988, 66, 1483; (d) E. L. Ahlsen and K. O. Stromme, Acta Chem. Scand., Ser. A, 1974, 28, 175.
6. F. Bigoli, P. Deplano, M. L. Mercuri, M. A. Pellinghelli and E. F. Trogu, Phosphorus Sulfur Silicon Relat. Elem., 1992, 70, 175.
7. F. Bigoli, P. Deplano, M. L. Mercuri, M. A. Pellinghelli and E. F. Trogu, Phosphorus Sulfur Silicon Relat. Elem., 1992, 72, 65.
8. F. L. Lu, M. Keshavarzk, G. Srdanov, R. H. Jacobson and F. Wudl, J. Org. Chem., 1989, 54, 2165.
9. F. Freeman, J. W. Ziller, H. N. Po and M. C. Keindl, J. Am. Chem. Soc., 1988, 110, 2568.
10. F. H. Herbstein and W. Schwotzer, J. Am. Chem. Soc., 1984, 106, 2367.
11. F. Cristani, F. Delmartin, F. A. Devillanova, F. Isaia, G. Saba and G. Verani, J. Chem. Soc., Dalton Trans., 1992, 3553.
12. A. J. Blake, F. A. Devillanova, A. Garu, F. Isaia, V. Lippolis, S. Parsons and M. Schröder, J. Chem. Soc., Dalton Trans., 1999, 525.
13. M. Arca, F. A. Devillanova, F. A. Garau, F. Isaia, V. Lippolis, G. Verani and F. Delmartin, Z. Anorg. Allg. Chem., 1998, 624, 745.
14. C. Knobler, C. Baker, H. Hope and J. D. McCullough, Inorg. Chem., 1971, 10, 697.
15. A. J. Arduengo and E. M. Burgess, J. Am. Chem. Soc., 1977, 99, 2376.
16. F. A. Devillanova, P. Deplano, F. Isaia, V. Lippolis, M. L. Mercuri, S. Piludu, G. Verani and F. Delmartin, Polyhedron, 1998, 17, 305.
17. F. Delmartin, P. Deplano, F. A. Devillanova, F. Isaia, V. Lippolis and G. Verani, Inorg. Chem., 1993, 32, 3694; D. L. Nosco, M. J. Hegg, M. D. Glick, R. C. Elder and E. Deutsch, J. Am. Chem. Soc., 1980, 102, 7784; G. H. Y. Lin and H. Hope, Chem. Commun., 1970, 169; Acta. Crystallogr., Sect. B, 1972, 28, 643; O. Hassel and H. Hope, Acta Chem. Scand., 1961, 15, 407.
18. J. Buxeraud, A. C. Absil, J. Claude, C. Raby, G. Catanzano and C. Beck, Eur. J. Med. Chem. Chim. Ther., 1985, 20, 43.
19. J. R. Ferraro and J. M. Williams, Introduction to Synthetic Electric Conductors, Academic Press, New York, 1987.
20. G. Steimecke, R. Kirmse and E. Hoyer, Z. Chem., 1975, 15, 28; G. Steimecke, H.-J. Sieler, R. Kirmse and E. Hoyer, Phosphorus Sulfur Relat. Elem., 1979, 7, 49.
21. N. Svenstrup and J. Becher, Synthesis, 1995, 215.
22. J. E. Huheey, Inorganic Chemistry: Principles of Structure and Reactivity, 3rd edn., Harper and Row, New York, 1983.
23. F. van Bolhuis, P. B. Koster and T. Migchelsen, Acta Crystallogr., 1967, 23, 940.
24. I. L. Karle, J. Chem. Phys., 1955, 23, 1739.
25. L. N. Swink and G. B. Carpenter, Acta Crystallogr., Sect. B, 1968, 24, 429.
26. L. E. Selin, Naturwissenschaften, 1960, 47, 104.
27. F. Bigoli, P. Deplano, F. A. Devillanova, V. Lippolis, M. L. Mercuri, M. A. Pellinghelli and E. F. Trogu, Eur. J. Inorg. Chem., 1998, 137; M. Arca, F. Demartin, F. A. Devillanova, A. Garau, F. Isaia, V. Lippolis, S. Piludu and G. Verani, Polyhedron, 1998, 17, 3111.
28. S. M. Godfrey, S. L. Jackson, C. A. McAuliffe and R. G. Pritchard, J. Chem. Soc., Dalton Trans., 1998, 4201.
29. E. Fanghänel, K. H. Kühnemund and A. M. Richter, Synth. Commun., 1984, 319.
30. K. N. Robertson, P. K. Bakshi, T. S. Cameron and O. Kemp, Z. Anorg. Allg. Chem., 1997, 623, 101.
31. B. Vonnegut and B. E. Warren, J. Am. Chem. Soc., 1936, 58, 2459; J. Donohue and S. H. Goodman, Acta Crystallogr., 1965, 18, 568.
32. C. W. Cunningham, G. R. Burns and V. McKee, Inorg. Chim. Acta, 1990, 167, 135.
33. C. R. Hubbard and R. A. Jacobson, Inorg. Chem., 1972, 11, 2247.
34. C. Freireedbrugger, D. Jentsch, P. G. Jones and E. Schwarzmann, Z. Naturforsch., Teil B, 1987, 42, 1553.
35. J. A. Darr, S. R. Drake, M. B. Hursthouse and K. M. A. Malik, Inorg. Chem., 1993, 32, 5704.
36. N. P. C. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, 39, 158.
37. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
38. G. M. Sheldrick, SHELXL 93, program for crystal structure refinement, University of Göttingen, 1993.