When the dominant packing type is window-to-arene, three different crystal structures are reported to exist experimentally (Fig. ), outlined in purple) which seemingly corroborates our window-to-arene results from the simulations that evidence a much richer phase diagram than for window-to-window. Yet, only two of the three experimentally known phases are found in our phase diagram, CC9-R3 (at σ ang = 0.6) (Fig. )) and CC1β ′ (at σ ang = 0.7) (Fig. ). The remaining phase reported experimentally does not exist within any of our phase diagrams. However, this is not a surprising result. Experimentally, this structure is formed with both cages CC3 and CC4 upon desolvation from another ordered structure. As such, it has been suggested that the crystal structure identified is formed due to a solvent templation effect, something not taken into account by our model, and so it is not expected to be found in our simulations. This result highlights the relationship that solvent can be used to alter the polymorphic behaviour of the crystal and even change the preference of the dominant interaction between facets. In this case, the change in packing behaviour for CC3 from CC3α to CC3β would likely decrease the porosity from the loss of the three dimensional pore network, however, for CC4 para-xylene can direct the packing behaviour from window-to-arene to window-to-window as seen in the formation of CC4β. While our results show that we can predict most of the crystal structures known to be formed by ordered, enantiopure, desolvated octahedral cages, there still remains two ordered phases produced in our window-to-arene simulations that do not match up to any of the structures in Table . The first of these structures is a novel phase (when σ ang = 0.5) (Fig. (e)) not reported within the literature, and the second is found in solvated forms of both CC3 with Et 2 O and CH 2 Cl 2 and CC4 with MeOH (Fig. (f)). Although we were not intending to find solvated structures, the occurrence of the solvated crystal in this region of phase space is logical as the structure occurs at low values of σ ang = 0.2 -0.4, which suggests the inclusion of the solvent increases the directionality as it occurs at small patch widths. This is a logical result as the inclusion of solvents is likely to make the intermolecular interactions more directional, analogous to decreasing σ ang . Moreover, this phase is the same as the solvated structure which produces CC3β/CC4α upon desolvation. An overview of where each experimental phase is found in our simulations is give in Table .