Mössbauer spectra of tin(IV) iodide complexes

Abstract
The first examples of compounds containing the [SnR2I3] anion, i.e. [Bun 4N][SnR2I3] (R = Me or Ph), have been prepared and characterized by IR, Raman and 119Sn Mössbauer spectroscopies, and X-ray powder diffraction data. The experimental data are consistent with a trigonal bipyramidal structure, with the R groups in equatorial positions, for the [SnR2I3] anions. Octahedral [SnR2I4]2– anions could not be isolated and it is shown that the previously reported [Bun 4N]2[SnMe2I4] is actually a 1∶1 mixture of Bun 4NI and [Bun 4N][SnMe2I3]. The X-ray powder structure of Cs2SnI6 has been refined by the Rietveld method. The compound crystallises in the cubic Fm3m space group with a = 11.6410(3) Å and a Sn–I distance of 2.864(1) Å. The Sn–I distances in Cs2SnI6, SnI4(bipy), SnI4(Ph3PO)2 and SnI4(Ph2SO)2 are related to the Mössbauer quadrupole splitting, showing that ligands that are weaker donors than I (i.e. have a more positive partial quadrupole splitting) give rise to Sn–I distances that are shorter than for the [SnI6]2– anion.

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