By growing a canonical Mott insulator (V2O3) on sapphire substrates with different orientations we can control the structural transition trajectory leading to huge changes in electronic and structural properties. In (a) we show a normal resistive transition for a V2O3 thin film, along with the corresponding lattice orientation of the film and its expansion direction during the transition. (b-d) reciprocal space maps obtained with x-ray diffractometry corresponding to (a), showing the structural transition from the corundum (metallic) structure to the monoclinic (insulating) structure as the sample is cooled. Conversely, in (e) the structural transition involves an in-plane expansion which is hindered for this lattice orientation due to the limited substrate area. Therefore, the resistive transition is very heavily suppressed (by a factor of >108) accompanied by a highly unusual reentrant metallic behavior at low temperature. Due to structural confinement the metallic phase persists down to very low temperatures (f-h), maintaining metallic percolation with self-induced stress of 2 GPa. This transition is analogous to the isochoric water-ice phase transition where, due to the constant volume, the two phases coexist as the transition progresses along the equilibrium line between the two phases. This self-induced stress allows access to previously inaccessible regions of the phase diagram. The switching properties of devices based on this unusual state of matter are currently being explored.