High-pressure Nucleation of Low-Density Polymorphs**

New polymorphs beta and gamma of bis-3-nitrophenyl disulphide, crystallized above 0.3 GPa, are less dense than the ambient-pressure polymorph alpha. This counterintuitive density relation results from the high-entropy nucleation and subsequent kinetic crystallization. The work performed by pressure compensates the high entropy and temperature product, substantiated in varied conformers and increased chemical potential. Pressure-increased viscosity promotes the kinetic polymorphs, in accordance with empirical Ostwald's rule of stages. It contrasts to mechanochemical techniques, favouring high-density polymorphs.

Automated summary

The new polymorphs beta and gamma of bis-3-nitrophenyl disulphide crystallized above 0.3 GPa are less dense than the ambient-pressure polymorph alpha, due to high-entropy nucleation and kinetic crystallization. Pressure-compensated high entropy and temperature product promotes varied conformers and increased chemical potential, resulting in kinetic polymorphs in accordance with Ostwald's rule of stages, contrasting with mechanochemical techniques favoring high-density polymorphs.