Untersuchungen an festem Dichlorhexoxid: Erste Kristallstrukturbestimmung an einem Chloroxid

Investigations on Solid Dichlorinehexaoxide: The First Crystal Structure Determination of a Chlorine Oxide Cl₂O₆ was synthesized by reaction of ClO₂ with O₂/O₃ mixtures and purified by trap-to-trap condensation. Crystal growth was achieved by sublimation (?5°C→ ?20°C) at p = 10^?4 bar on a cold finger. The crystal structure was solved using diffractometer data (Cc; a = 556.3(2), b = 861.3(3), c = 978.5(3) pm, β = 100.56(5)°; Z = 4; MoKα; ?70°C; 666 independent reflections; 71 variable parameters; R_w = 2,46%). In the solid state Cl₂O₆ is ionically mixed-valent which can be expressed by the formula ClO₂⁺ClO₄^?. The arrangement of the compound anions and cations derives from the CsCl type of structure. Raman and infrared spectra of solid Cl₂O₆ have been recorded and an assignement of the observed spectra is proposed.