Structures of the BrF(4)(+) and IF(4)(+) cations.

The large discrepancies between the calculated and observed structures for BrF(4)(+) and IF(4)(+) (Christe, K. O.; Zhang, X.; Sheehy, J. A.; Bau, R. J. Am. Chem. Soc. 2001, 123, 6338) prompted a redetermination of the crystal structures of BrF(4)(+)Sb(2)F(11)(-) (monoclinic, P2(1)/c, a = 5.2289(6) A, b = 14.510(2) A, c = 14.194(2) A, beta = 90.280(1) degrees, Z = 4) and IF(4)(+)SbF(6)(-) (orthorhombic, Ibca, a = 8.2702(9) A, b = 8.3115(9) A, c = 20.607(2) A, Z = 8). It is shown that for BrF(4)(+), the large differences were mainly due to large errors in the original experimental data. For IF(4)(+)SbF(6)(-), the geometry previously reported for IF(4)(+) was reasonably close to that found in this study despite a very large R-factor of 0.15 and a refinement in an incorrect space group. The general agreement between the calculated and the redetermined geometries of BrF(4)(+) and IF(4)(+) is excellent, except for the preferential compression of one bond angle in each ion due to the influence of interionic fluorine bridges. In BrF(4)(+), the fluorine bridges are equatorial and compress this angle. In IF(4)(+), the nature of the fluorine bridges depends on the counterion, and either the axial (in IF(4)(+)SbF(6)(-)) or the equatorial (in IF(4)(+)Sb(2)F(11)(-)) bond angle is preferentially compressed. Therefore, the geometries of the free ions are best described by the theoretical calculations.