Polymorphism of a widely used building block for halogen-bonded assemblies: 1,3,5-trifluoro-2,4,6-triiodobenzene

After reporting the structure of a new polymorph of 1,3,5-trifluoro-2,4,6-triiodobenzene (denoted BzF3I3), C6F3I3, (I), which crystallized in the space group P2(1)/c, we perform a comparative analysis with the already reported P2(1)/n polymorph, (II) [Reddy et al. (2006). Chem. Eur. J. 12, 2222-2234]. In polymorph (II), type-II I center dot center dot center dot I halogen bonds and I center dot center dot center dot pi interactions connect molecules in such a way that a three-dimensional structure is formed; however, the way in which molecules are connected in polymorph (I), through type-II I center dot center dot center dot I halogen bonds and pi-pi interactions, gives rise to an exfoldable lamellar structure, which looks less tightly bound than that of (II). In agreement with this structural observation, both the melting point and the melting enthalpy of (I) are lower than those of (II).