Structure and reactivity of pyridine crystal under pressure

In this work we have performed an extensive high pressure study of the condensed phases of pyridine by Raman and IR spectroscopy. We have evidenced three different polymorphs, two crystalline, and one glassy and established the pressure conditions in which they exist as stable or metastable phases by several compression/decompression experiments both on annealed and not annealed samples. Crystallization and phase transitions are found to be kinetically driven. The vibrational spectra are extremely complex due to the low symmetry of the crystals, which implies a large number of crystal components. This complexity required a careful analysis of both IR and Raman data that led to the identification of 20 out of 21 external modes expected for phase II. We did not find any conclusive indication of phase transitions on compressing phase II thus indicating that phase II is likely the stable phase at the onset pressure of the chemical transformation of pyridine. The latter starts at 18 GPa and relevant differences from the well characterized benzene reaction suggest that it is likely driven by crystal defects.