Solution crystallisation via a submerged liquid–liquid phase boundary: oiling out

In many situations the process of crystallisation from solution is known to occur via metastable crystalline states (polymorphs or solvates). Here we present what we believe to be a novel example of small molecule crystallisation in which the initial separation of a solute rich liquid phase precedes the crystallisation event. We believe this occurs because a submerged liquid–liquid phase boundary is accessible within the metastable zone of the crystal nucleation process.