N1-N2 N1-P1 For structures containing >1 crystallographically independent molecules: one representative value is provided if there is no statistically significant difference (3σ); values for each molecule are provided if there is a statistical difference. a) Crystal structures previously reported but selected bond distances and angles provided for comparison. The structure of azophosphine 1-OMe has N1-N2 and N1-P1 bond lengths of 1.2560(17) Å and 1.7660(13) Å, respectively, and is analogous to the previously reported 1-NMe2. The pyramidal geometry at phosphorus for 1-OMe is reflected in the sum of the angles around P1 (307.9°), which highlights that the lone pair on phosphorus will be available for further reactivity and coordination chemistry.