Synthesis and Characterisation of Ionic Ozonides with Bisquaternary Ammonium Counterions

The bisquaternary ammonium ozonides Me3N+(CH2)n +NMe3(O3‐)2 with n = 3, 4, 6 (1, 2, 3), Me3N+(CH2)3+NMe3(O3‐)2 · 3 NH3 (1a), Me3N+(p‐Ph)+NMe3(O3‐)2 (4) and Me3N+(p‐Ph)+NMe3(O3‐)2 · NH3 (4a) were obtained in quantitative yields by cation exchange starting from CsO3. The compounds 1a and 3 have been studied by single crystal X‐ray analysis. The influence of C–H…O and N–H…O hydrogen bonds on the bond length and the bond angle of the ozonide anion is discussed; earlier results are included. The difference between the two bond lengths within the O3‐ ion [137.4(3) pm and 129.5(3) pm] in 1a is unexpectedly large. Thermal stabilities determined by DTA/TG methods range from 24–83°C.