Weak Interactions in TKX‐50 Molecule Crystal

ABSTRACT To conduct a comprehensive analysis of the weak interactions among the fragments in the dihydroxylammonium 5,5′‐bistetrazole‐1,1′‐diolate (TKX‐50) molecular crystal, a bis‐tetrazolium fragment was chosen as the central fragment interest, analyzing the Hirshfeld surfaces, fingerprint plots, dispersion density and the independent gradient model based on Hirshfeld partition (IGMH) between the atoms in this fragment and other surrounding fragment's atoms based on the theory calculation level of PBE/DZVP‐MOLOPT‐GTH, summing up the interactional type and strength and comparing them with that in the gaseous TKX‐50 molecules. The results revealed that the range of weak interaction within the crystal was narrower than that in the molecules, and the characteristic π⋯π stacking originated from the interactions of four atom pairs: two pairs of C⋯N and two pairs of N⋯N between two face‐to‐face tetrazole rings. These characteristics principally arise frodm two factors: (1) The final balance is achieved when more reciprocal interactions are exerted on the atoms of various fragments during the stacking process, from TKX‐50 molecules to crystals. (2) The attraction of electrons, proposed by the stronger electronegativity of the O atoms bonded to the bis‐tetrazolium fragments, results in the deviation of the electron density of the tetrazole rings to the side of O and eventually forms the π⋯π stacking, as demonstrated in this study.