The interaction between hexabromoethane and [CpRu(CO)(2)Br] (Cp = (eta-C5H5), results in the deposition of two different isostoichiometric co-crystals, 2[CpRu(CO)(2)Br]center dot C2Br6, one crystallising in space group P (1) over bar (Z = 1) and the other in P2(1)/n (Z = 4). These were produced in the reaction of HCBr3 and [(CpRu(CO)(2))(2)] under indoor illumination, following a slight modification of the literature procedure. The origin of the hexabromoethane is as yet unknown but it appears to have been formed in the reaction rather than being an impurity in the bromoform. We have analysed the structures using the Hirshfeld surface approach and electrostatic potentials, supported by DFT theoretical calculations to better define the nature of intermolecular interactions in the solid state. The results indicate that the most significant interactions within both crystal forms arise not from the closest van der Waals contacts but, rather, from more distant interactions between the unsymmetrical electron distributions about the bromine atoms in the solvate and substrate molecules.