High-energetic and low-sensitive 1,3,5-triamino 2,4,6-trinitrobenzene (TATB) crystal: first principles investigation and Hirshfeld surface analysis†

First principles investigation and Hirshfeld surface analysis of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystals have been carried out. The geometrical and electronic structures of TATB molecules in the crystal and gas phases were compared. The Hirshfeld surface analysis of the TATB crystal structure shows that the intermolecular HMIDLINE HORIZONTAL ELLIPSISO interactions make important contributions in stabilizing the TATB crystal, while other intermolecular HMIDLINE HORIZONTAL ELLIPSISN and HMIDLINE HORIZONTAL ELLIPSISC interactions, OMIDLINE HORIZONTAL ELLIPSISO, NMIDLINE HORIZONTAL ELLIPSISO, CMIDLINE HORIZONTAL ELLIPSISO, and CMIDLINE HORIZONTAL ELLIPSISN close contacts also make contributions. QTAIM analyses of the intermolecular interactions in the molecular pairs confirm the presence of these intermolecular interactions based on Hirshfeld surface analyses, indicating that these intermolecular interactions play important roles in the crystal. The reason why the TATB crystal adopts a high energy conformer in which the NO2 and NH2 groups are coplanar with the benzene ring is elaborated. The cooperativity between hydrogen bonding and pi MIDLINE HORIZONTAL ELLIPSIS pi interactions in the TATB crystal is verified and illustrated.

Automated summary

By conducting first principles investigation and Hirshfeld surface analysis, the study revealed the significance of intermolecular interactions in TATB crystals, as well as the influence of hydrogen bonding and π-π interactions on the TATB crystal.