Halogen-rich halorhenates(IV): (Me4N)2{[ReX6](X2)} (X = Cl, Br)

Dihalogen - halorhenates(IV) (Me4N)2{[ReX6](X2)} (X = Cl (1), Br (2)) were prepared and structurally characterized, featuring the first examples of rhenium/dihalogen supramolecular complexes. 1 and 2 reveal pseudo-3D structure; both compounds demonstrate high thermal stability, releasing Cl2 or Br2 only at elevated temperatures (over 90 and 150 °C, respectively). The energies of halogen···halogen non-covalent interactions were estimated to be as high as 2.5 and 5.1 kcal/mol for 1 and 2, respectively. Hirshfeld surface analysis was performed for both structures, allowing estimation of contributions of different non-covalent interactions to crystal packing.