A transient metastable rotator phase occurring on crystallization of hexadecane into its triclinic phase from the supercooled melt was directly observed with time-resolved synchrotron x-ray scattering. In this system, the limit of supercooling (the crystallization temperature) is determined by the thermodynamic stability of the transient phase with respect to the Liquid. The crystallization kinetics of the homologous series of n-alkanes was measured and explained in terms of a crossover from stability to "long-lived" metastability to transient metastability. This crossover allowed further confirmation of the nature of the transient phase.