The recent experimental characterization of a 3D polybromide network containing the octahedral complex anion Br (Br-2)(6) by Feldmann's group [Wolff et al., Angew. Chem., Int. Ed. 50 (2011) 4970] sparked our interest to investigate the structures and bonding in Br (Br-2)(n) complexes, n = 1-6, with the aid of quantum mechanical calculations. The quantum theory of atoms in molecules (QTAIM) indicates the presence of closed-shell interactions between dibromine molecules and the bromide anion. (C) 2011 Elsevier B.V. All rights reserved.