Reactive metal-ligand (M-L) multiply bonded complexes are ubiquitous intermediates in redox catalysis and have thus been long-standing targets of synthetic chemistry. The intrinsic reactivity of mid-to-late M-L multiply bonded complexes renders these structures challenging to isolate and structurally characterize. Although synthetic tuning of the ancillary ligand field can stabilize M-L multiply bonded complexes and result in isolable complexes, these efforts inevitably attenuate the reactivity of the M-L multiple bond. Here, we report the first direct characterization of a reactive Ru2 nitride intermediate by photocrystallography. Photogeneration of reactive M-L multiple bonds within crystalline matrices supports direct characterization of these critical intermediates without synthetic derivatization.