High-density HNIW/TNT cocrystal synthesized using a green chemical method

The main challenge for achieving better energetic materials is to increase their density. In this paper, cocrystals of HNIW (2,4,6,8,10,12-hexa­nitro-2,4,6,8,10,12-hexa­aza­isowurtzitane, often referred to as CL-20) with TNT (2,4,6-tri­nitro­toluene) were synthesized using ethanol in a green chemical method. The cocrystal was formulated as C(13)H(11)N(15)O(18) and possesses a higher density (1.934 g cm(−3)) than published previously (1.846 g cm(−3)). This high-density cocrystal possesses a new structure, which can be substantiated by the different types of hydrogen bonds. The predominant driving forces that connect HNIW with TNT in the new cocrystal were studied at ambient conditions using single-crystal X-ray diffraction, powder X-ray diffraction, Fourier transform–infrared spectroscopy and Raman spectroscopy. The results reveal that the structure of the new HNIW/TNT cocrystals consists of three one-dimensional hydrogen-bonded chains exploiting the familiar HNIW–TNT multi-component supramolecular structure, in which two hydrogen-bonded chains are between —NO(2) (HNIW) and —CH (TNT), and one hydrogen-bonded chain is between —CH (HNIW) and —NO(2) (TNT). The changes to the electron binding energy and type of element in the new cocrystal were traced using X-ray photoelectron spectroscopy. Meanwhile, the physicochemical characteristics alter after cocrystallization due to the hydrogen bonding. It was found that the new HNIW/TNT cocrystal is more thermodynamically stable than HNIW. Thermodynamic aspects of new cocrystal decomposition are investigated in order to explain this observation. The detonation velocity of new HNIW/TNT cocrystals is 8631 m s(−1), close to that of HNIW, whereas the mechanical sensitivity is lower than HNIW.