The excluded volume of a pair of molecules is proportional to the second virial coefficient in hard-core models that represent, for instance, the reference model in perturbation approaches to statistical theories of fluids [see, e.g. Chap. 5 of Kalikmanov, V. (2001), Statistical Physics of Fluids. Texts and Monograph in Physics, Springer, Berlin]. In three space dimensions, there exist exact results for convex molecules and in fact lack of convexity has been a major obstacle in applying the mathematical techniques employed in the convex case. In this paper, we illustrate how a mixed—analytical and numerical—method can be used to obtain exact expressions of the excluded volume for a pair of non-convex molecules conceived as aggregates of hard spheres; these can model van der Waals regions associated to the atoms forming each molecule. To compute the excluded volume for molecules endowed with C2v symmetry, modelled as chains of tangent hard spheres, we adapt a numerical code available to the scientific community. Because the result is a rather cumbersome expression in term of the relative orientation of the interacting molecules, we expand it over a suitable set of symmetry adapted Wigner functions to build up approximate, but faithful expressions, and we also prove analytical results announced elsewhere [Bisi, F., Durand, G., Rosso, R. & Virga, E. (2008), Polar steric interactions for v-shaped molecules. Phys. Rev. E, 78, 011705].