Abstract
A one-step synthesis of an oxime-bridged nitropyrazole–tetrazole yields two concomitant polymorphs, planar 3-α and twisted 3-β. Their contrasting solid-state geometries give rise to distinct packing, π-delocalization, and thermal stability. Both exhibit RDX-like detonation performance, demonstrating oxime bridging as an effective strategy for thermally stable, safer high-performance energetic materials.