Two isostructural energetic cocrystals containing 1,3,5-trinitrobenzene (TNB) were obtained with the energetic materials 1,3,5-triiodo-2,4,6-trinitrobenzene (TITNB) and 1,3,5-tribromo-2,4,6-trinitrobenzene (TBTNB) in ratios of 2:1 TNB/TITNB (1) and 2:1 TNB/TBTNB (2). These materials contain the shortest nitro–iodo and second shortest nitro–bromo interactions seen in the Cambridge Structural Database for organohalides. Computational studies indicate that the cocrystals are more stable than their respective component crystals by 11.5 kJ/mol for 1 and 8.2 kJ/mol for 2. While the formation of an isostructural 2:1 cocrystal with 1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB) was calculated to be favorable by 8.5 kJ/mol, only a physical mixture of the two coformers was obtained experimentally. Both 1 and 2 possess high crystallographic densities (2.203 and 1.980 g/cm³, respectively) and were found to be insensitive in small-scale impact drop tests, possessing sensitivity between that of TNB and TXTNB (X = I or Br). The halogen content of the two cocrystals suggests application as insensitive biocidal energetics. Halogen bonding, facilitated by the strong polarization induced by aromatic ring nitration, plays a critical role in the formation of these cocrystals and offers a promising route to the development of new energetic cocrystals.

中文翻译：

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1,3,5-三硝基苯通过卤素键组装的同构共晶体

获得了两个含1,3,5-三硝基苯（TNB）的同构高能共晶体，以及高能材料1,3,5-三碘代-2,4,6-三硝基苯（TITNB）和1,3,5-三溴-2。比例为2：1 TNB / TITNB（1）和2：1 TNB / TBTNB（2）的4,6-三硝基苯（TBTNB ）。这些材料包含在有机卤化物的剑桥结构数据库中看到的最短的硝基-碘相互作用和次短的硝基-溴相互作用。计算研究表明，共结晶比它们各自的组分晶体更稳定的11.5千焦/摩尔为1和8.2千焦/摩尔2。虽然计算出与1,3,5-三氯-2,4,6-三硝基苯（TCTNB）形成的同构2：1共晶体有利于8.5 kJ / mol，但仅获得了两种共形成剂的物理混合物实验上。既1和2具有较高的结晶密度（2.203和1.980克/厘米³，并在小规模的跌落试验中被发现不敏感，其灵敏度在TNB和TXTNB之间（X = I或Br）。这两种共晶体的卤素含量表明其可作为不敏感的杀生物能。芳香环硝化引起的强极化促进了卤素键的形成，在这些共晶体的形成中起着至关重要的作用，并为开发新的高能共晶体提供了有希望的途径。