Sun Shanhu, Zhang Haobin, Xu Jinjiang, Wang Hongfan, Wang Shumin, Yu Zhihui, Zhu Chunhua, Sun Jie
Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, Sichuan, People's Republic of China.
School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, Sichuan, People's Republic of China.
Acta Crystallogr B Struct Sci Cryst Eng Mater. 2019 Jun 1;75(Pt 3):310-317. doi: 10.1107/S2052520619002816. Epub 2019 May 9.
2,4,6,8,10,12-Hexanitrohexaazaisowurtzitane (CL-20)-based cocrystals have gained increasing attention as a means of obtaining insensitive high explosives. However, the design of ideal candidates for these cocrystals remains difficult. This work compares the crystal energies of the CL-20-dinitrobenzene (DNB) and CL-20-2,4,6-trinitrotoluene (TNT) cocrystals with those of the respective pure coformers. The results indicate that the cocrystal formation is driven by the differences in the energies of the cocrystals and the coformers. Furthermore, analysis via Hirshfeld surfaces and two-dimensional fingerprint plots confirms that the O...O, O...H, O...N and C...O interactions were the main force for stabilizing the CL-20-based cocrystal structure. Based on these findings, a novel energetic-energetic cocrystal of CL-20-2,4,6-trinitrophenol (TNP) was designed and prepared by means of a rapid method for solvent removal. The crystal structure was investigated via powder X-ray diffraction methods, solid-state nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy. The results revealed that the O-H...O hydrogen bonding interaction between the phenolic hydroxyl group of TNP and nitro groups of CL-20, as well as nitro...π, nitro...nitro and O...π(N) interactions, based on the benzene ring and nitro groups, are the main interactions occurring in the cocrystal.
基于2,4,6,8,10,12-六硝基六氮杂异伍兹烷（CL-20）的共晶体作为一种获得钝感高能炸药的手段受到了越来越多的关注。然而，为这些共晶体设计理想的候选物仍然很困难。这项工作将CL-20-二硝基苯（DNB）和CL-20-2,4,6-三硝基甲苯（TNT）共晶体的晶体能量与各自纯共晶形成物的晶体能量进行了比较。结果表明，共晶体的形成是由共晶体和共晶形成物能量的差异驱动的。此外，通过 Hirshfeld 表面和二维指纹图谱分析证实，O...O、O...H、O...N 和 C...O 相互作用是稳定基于 CL-20 的共晶体结构的主要作用力。基于这些发现，通过一种快速的溶剂去除方法设计并制备了一种新型的 CL-20-2,4,6-三硝基苯酚（TNP）高能-高能共晶体。通过粉末 X 射线衍射方法、固态核磁共振光谱和傅里叶变换红外光谱对晶体结构进行了研究。结果表明，TNP 的酚羟基与 CL-20 的硝基之间以及基于苯环和硝基的硝基...π、硝基...硝基和 O...π(N)相互作用的 O-H...O 氢键相互作用是共晶体中发生的主要相互作用。
