Polymorphism and Hirshfeld surface analysis of tetraoxa[2]perfluoroarene[2]triazine

The title compound, tetra-oxa[2]perfluoro-arene[2]triazine (C₂₀H₆F₈N₆O₆), composed of two tetra-fluoro-phenyl-ene and two triazine moieties connected by four oxygen atoms, was crystallized <i>via</i> slow evaporation of a di-chloro-methane solution, yielding two polymorphs: block- (<b>I</b>) and plate-shaped (<b>II</b>) crystals. Polymorph <b>I</b> (triclinic, <i>P</i>1, <i>V</i> = 516 ų at 173 K) was previously reported by Yang <i>et al.</i> [(2015. <i>Org. Lett.</i> <b>15</b>, 4414-4417] whereas the newly identified polymorph <b>II</b> (triclinic, <i>P</i>1, <i>V</i> = 1085 ų at 100 K) shares the same space group but has a unit-cell volume twice as large, accommodating two symmetrically distinct mol-ecules, <i>Mol-ecule-1</i> and <i>Mol-ecule-2</i>, with a different mol-ecular arrangement. Since these crystals are expected to exhibit the characteristics of non-porous adaptive crystals, detailed analyses of inter-molecular inter-actions were conducted, revealing that C-F⋯π-hole inter-actions are more pronounced in <b>II</b> than in <b>I</b>. Hirshfeld surface analysis at 100 K revealed that the primary contributions to the crystal packing in polymorph <b>I</b> were F⋯F (17.1%), F⋯H/H⋯F (21.5%), C⋯H/H⋯C (6.3%), C⋯F/F⋯C (4.5%) and C⋯O/O⋯C (9.2%) inter-actions, whereas in polymorph <b>II</b>, these inter-actions were F⋯F (9.9% and 10.0%), F⋯H/H⋯F (20.9% and 26.5%), C⋯H/H⋯C (6.3% and 2.9%), C⋯F/F⋯C (8.5% and 10.0%) and C⋯O/O⋯C (4.9% and 4.6%) for <i>Mol-ecule-1</i> and <i>Mol-ecule-2</i>, respectively. Powder X-ray diffraction analysis indicates that polymorph <b>I</b> is the more stable crystalline form, predominantly obtained through rapid precipitation or by grinding the crystals.