Can a heavy trinitromethyl group always result in a higher density?

Abstract

Density is an important property of energetic materials and is believed to increase with the addition of heavy trinitromethyl groups, as shown in previous literature. However, this study determined that the introduction of these groups produced a decrease in density, as evidenced by the lower density of 1-trinitromethyl-4-amino-3,5-dinitropyrazole ((TN-116), 1.899 g cm⁻³) compared to that of its precursor (4-amino-3,5-dinitropyrazole (LLM-116), 1.900 g cm⁻³). Mechanistic studies indicated that the reduced density was due to the significantly weaker H-bonding and π–π interactions of TN-116, which produced looser stacking compared to that of LLM-116.