Naph₂Sb₂1 was synthesized by a reaction of 1,8-dilithionaphthalene NaphLi₂ with SbCl₃ and its solid state structure is reported on. 1 shows intermolecular interactions in the solid state, which were studied by quantum chemical calculations with dispersion corrected density functional theory, supermolecular ab initio approaches and symmetry adapted perturbation theory. The same methods were employed to compare the solid state interactions in the crystal of 1 to those in real (for E = P) and hypothetical (for E = As and Bi) crystal structures of Naph₂E₂. Dispersion interactions were found to provide the most important stabilising contribution in all cases, seconded by electrostatic attraction between pnictogen atoms and π-systems of neighbouring naphthyl groups.