Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph

Abstract

Abstract We report on the syntheses and single-crystal structure determinations of the compounds A 2SiF6 (A = Tl, Rb, Cs). In comparison to the previous powder-based structure models we achieved more precise atom positions and distances. The compounds crystallize in the K2PtCl6 structure type, space group Fm 3 ‾ $‾{3}$ m (No. 225, cF36) with a = 8.4749(10) Å, V = 608.7(2) Å3, Z = 4 at T = 100 K for Tl2SiF6, a = 8.3918(10) Å, V = 591.0(2) Å3, Z = 4 at T = 100 K for Rb2SiF6, and a = 8.8638(11) Å, V = 696.4(3) Å3, Z = 4 at T = 200 K for Cs2SiF6. For the compound Tl3[SiF6]F we present a previously unknown tetragonal modification and correct the crystal structure of its trigonal modification to hexagonal. The tetragonal one crystallizes in the (NH4)3[SiF6]F structure type, space group P4/mbm (No. 127, tP22) with a = 8.0313(8), c = 5.8932(6) Å, V = 380.13(7) Å3, Z = 2, T = 298 K, and the crystal structure of the hexagonal modification is best described in space group P63 mc (No. 186, hP22) with a = 7.8248(4), c = 6.8768(4) Å, V = 364.64(4) Å3, Z = 2, T = 100 K.