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The melting diagram of the superacid system SbF 5 —CF 3 SO 3 H as well as of SbF 5 —HF has been studied by DTA and the crystal structure of one newly found low-melting adduct in each case determined. The adduct SbF 5  · CF 3 SO 3 H (m.p. — 1°C, monoclinic, space group P21/c, Z = 4 formula units per unit cell) is composed of complex molecules F 5 SbOS(CF 3 )(O)OH which are linked by strong hydrogen bonds O-H ···F to infinite chains. The adduct SbF 5  · 7HF (melting incongruently at —75°C, monoclinic, I 2/m, Z = 2) is a fluoronium salt, (H 7 F 6 )SbF 6 . The novel H 7 F 6  +  cation is formed as an unbranched chain by very strong hydrogen bonds between the respective F atoms, which become weaker from the center to the ends. A further hydrogen bond of this kind, between the cations and the octahedral SbF 6 - anions, again leads to a one-dimensional polymer.

zeitschrift für naturforschung b

Zur Kristallchemie von Supersäuren: Bildung und Struktur der tiefschmelzenden Addukte SbF 5  · CF 3 SO 3 H und SbF 5  · 7 HF [1] / Crystal Chemistry of Superacids: Formation and Structure of the Low-Melting Adducts SbF 5  · CF 3 SO 3 H and SbF 5  · 7 HF [1]