Crystal Structure Determination of the Pentagonal‐Pyramidal Hexamethylbenzene Dication C₆(CH₃)₆²⁺

In contrast to the well‐known 2‐norbornyl cation, the structure of which was a matter of long debate until its pentacoordinated nature was recently proven by an X‐ray structure, the pentagonal‐pyramidal dication of hexamethylbenzene has received considerably less attention. This species was first prepared by Hogeveen in 1973 at low temperatures in magic acid (HSO 3 F/SbF 5 ), for which he proposed a non‐classical structure (containing a hexacoordinated carbon) based on NMR spectroscopy and reactivity studies, but no X‐ray crystal structure has been reported. C 6 (CH 3 ) 6 2+ can be obtained through the dissolution of hexamethyl Dewar benzene epoxide in HSO 3 F/SbF 5 and crystallized as the SbF 6 − salt upon addition of excess anhydrous hydrogen fluoride. The crystal structure of C 6 (CH 3 ) 6 2+ (SbF 6 − ) 2 ⋅HSO 3 F confirms the pentagonal pyramidal structure of the dication. The apical carbon is bound to one methyl group (distance 1.479(3) Å) and to the five basal carbon atoms (distances 1.694(2)–1.715(3) Å).