A labile organoazide iron complex is reported. Under ambient conditions, the azide adduct is subject to a dissociation equilibrium in solution, yet also undergoes intramolecular C-H bond amination. Single-crystal irradiation of the azide at 80 K leads to partial N2-extrusion and formation of a putative imido iron intermediate, which was computationally identified as a highly covalent {FeNR}8 species.