Almost 200 years ago, benzamide was reported as polymorphic with two of its forms (II and III) found to be of difficult crystallisation. In a recent study, it was shown that benzamide form I can easily convert into benzamide form III with mechanochemistry in the presence of nicotinamide. Here we show, experimentally and computationally, that this transformation is the result of a thermodynamic switch between these two polymorphic forms driven by the formation of solid solutions with small amounts of nicotinamide. The presence of nicotinamide in the crystallisation environment promotes the robust and exclusive crystallisation of the elusive form III. These results represent a promising route to the synthesis and
utilisation of elusive polymorphs of pharmaceutical interest.