[K(crypt‐222)]+ (1) and [K(crypt‐222)]+ (3) are isostructural, displaying nearly identical unit cell parameters. The two structures are similar to the extent that the previously reported [K(crypt‐222)]+ model can be refined against the new data for [K(crypt‐222)]+ , with extra electron density being observed from the fourth fluorine atom of the . In agreement with experimental observations, theoretical calculations suggest that deprotonated [K(crypt‐222)]+ is highly unstable even at as low as 195 K. The previously considered 1:1 CHF3 clathrate of deprotonated [K(crypt‐222)]+ (crystallographically indistinguishable from 1) is ruled out on the basis of all available data.