The cocrystals (CH3)(3)As center dot C6F5I (1) and (CH3)(3)Sb center dot C6F5I (2) were generated in situ from equimolar mixtures of their components. 1 and 2 show very close I center dot center dot center dot As and I center dot center dot center dot Sb directional intermolecular interactions. They are 0.5 and 0.7 angstrom shorter than the sums of van der Waals radii, respectively, and are the shortest C-I center dot center dot center dot As and C-I center dot center dot center dot Sb halogen bonds of this type found for experimentally characterized molecular (co)crystals. Comparisons of the packing motifs and contacts in 1 and 2 with those in (CH3)(3)As (3), (CH3)(3)Sb (4) and C6F5I (5) illustrate the occurrence and hierarchy of the specific interactions. The heteromolecular components in 1 and 2 are assembled by I center dot center dot center dot As, I center dot center dot center dot Sb and F center dot center dot center dot H interactions. There are no significant intermolecular As center dot center dot center dot As contacts in 3, but Sb.Sb interactions in 4. Molecules in 5 are mainly associated by I center dot center dot center dot F, F center dot center dot center dot F and F center dot center dot center dot C contacts. The intermolecular interactions observed in the (co)crystals correspond to the calculated electrostatic potentials.