We report the multistep synthesis of a new array of 4,5-annelated bicyclic sydnone imine – (6-cyano-1-substituted-[1,2,3]oxadiazolo[5,4-b]pyridin-1-ium-5-yl)amide hydrochlorides. These bicyclic compounds are featured with the mesomeric charge spread out over the two fused aromatic fragments. Thus, these molecules can be considered as a new type of sydnone imine. The molecular structures of the bicyclic compounds were investigated in detail by X-ray and 1H, 13C, and 15N NMR studies. In addition, the characterization of these compounds and their synthetic intermediaries was undertaken to ascertain their effectiveness as potential plant stress protectants or herbicides.