Abstract
The first examples of compounds containing the [SnR2I3]– anion, i.e. [Bun4N][SnR2I3] (R = Me or Ph), have been prepared and characterized by IR, Raman and 119Sn Mossbauer 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 [Bun4N]2[SnMe2I4] is actually a 1∶1 mixture of Bun4NI and [Bun4N][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) A and a Sn–I distance of 2.864(1) A. The Sn–I distances in Cs2SnI6, SnI4(bipy), SnI4(Ph3PO)2 and SnI4(Ph2SO)2 are related to the Mossbauer 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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