The first single-crystal X-ray diffraction study of 2,6-diaziadamantane (2), a compound containing two diazirine functionalities, and B3LYP/6-311+G* and MP2/6-311+G* calculations relating to the interaction between carbon-nitrogen and nitrogen-nitrogen covalent bonds and electron density within the diazirine rings have been performed. In addition, the protonation of 2-aziadamantane (1) has been investigated. The single-crystal X-ray diffraction study of 2, including UV/vis titrations of 1, corroborate the theoretical conclusion that the low basicity can be attributed to a rehybridization of the nitrogen lone pairs. Moreover, the strain in diazirine is unusually small.