High-pressure behavior and Hirshfeld surface analysis of nitrogen-rich materials: triazido-s-triazine (TAT) and triazido-s-heptazine (TAH)

Triazido-s-triazine (TAT) and triazido-s-heptazine (TAH) are two kinds of effective nitrogen-rich precursors for carbon nitride nanomaterials and potential high-energy density materials. In this work, the high-pressure behavior (0–500 GPa) and Hirshfeld surface of crystalline TAT and TAH were studied in details to better compare and reveal their stabilities. Crystal and molecular structures of TAT and TAH largely changed with the increase in pressure. The distortion of rings happens at 171 GPa for TAT and 483 GPa for TAH. The azide/tetrazole (AZ/TZ) isomerization happens in crystalline TAT, and the tetrazole ring forms at 266 GPa for the first time, while this phenomenon has not been observed in crystalline TAH during the whole process. Hirshfeld surface analyses intuitively show that: (1) both compounds possess the planar conjugated molecular structures; (2) N…N nonbonding interactions contribute a lot to stabilize their crystal packings; and (3) TAH is much more resistant to high pressure and more stable than TAT. The systematic investigation gives a guidance to understand the physical and chemical behaviors of nitrogen-rich azidoheterocyclic materials.