Towards low-impact-sensitivity through crystal engineering: New energetic co-crystals formed between Picric acid, Trinitrotoluene and 9-Vinylanthracene

Sen N., Dursun H., Hope K. S., NAZIR H., ACAR N., ATAKOL O.

JOURNAL OF MOLECULAR STRUCTURE, cilt.1219, 2020 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 1219
  • Basım Tarihi: 2020
  • Doi Numarası: 10.1016/j.molstruc.2020.128614
  • Dergi Adı: JOURNAL OF MOLECULAR STRUCTURE
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Chimica, Compendex, INSPEC
  • Anahtar Kelimeler: Picric acid, Trinitrotoluene, Impact sensitivity, Crystal engineering, Energetic co-crystals, Detonation performance, INTERMOLECULAR INTERACTIONS, HYDROGEN-BOND, PI-STACKING, COCRYSTAL, PACKING, GROWTH, PERFORMANCE
  • Ankara Üniversitesi Adresli: Evet

Özet

New 1:1 energetic co-crystals formed between Picric acid, Trinitrotoluene and 9-Vinylanthracene were prepared by a solvent evaporation method. The structures of the co-crystals were determined and characterized via single-crystal and powder X-ray diffraction techniques, infrared spectroscopy and thermal analysis (DSC, TG). X-ray diffraction results show that the co-crystals are mainly formed through host-guest pi center dot center dot center dot pi stacking with aid of intermolecular hydrogen bonding (C-H center dot center dot center dot N, C-H center dot center dot center dot O). Hirshfeld surfaces and associated fingerprint plots of the co-crystals were examined and the results indicated that the structures are stabilized by H center dot center dot center dot H (30.1% and 33.3%), O center dot center dot center dot H (24.3% and 19.5%), O center dot center dot center dot O (4.6% and 1.8%), C center dot center dot center dot H (3.8% and 5.3%) and C center dot center dot center dot C (6.8% and 6.8%) intermolecular interactions for PIC: VANT and TNT: VANT respectively. The use of Hirshfeld surfaces in combination with fingerprint plots demonstrates that these weak interactions are important for both local packing and crystal packing. The enthalpies of formation, the optimized structures, molecular total energies, frontier orbit energies, and HOMO-LUMO gaps of each compound were calculated using Gaussian 09; and detonation performances were calculated using the EXPLO5 software package. The co-crystals were found to be less impact-sensitive than Trinitrotoluene and Picric acid. This dramatic difference in co-crystal sensitivities may stem from the significantly different pi-stacking, hydrogen bonding interactions, crystal packing, O center dot center dot center dot O interactions, HOMO-LUMO gaps, free space in crystal lattice, and the electrostatic potential surface properties seen in both co-crystal structures. These results highlight an important consideration in the design of future Trinitrotoluene and Picric acid energetic co-crystals, and the feasibility of improving sensitivity properties through co-crystallisation. (C) 2020 Elsevier B.V. All rights reserved.