Sublimation of pyridine derivatives: fundamental aspects and application for two-component crystal screening

Abstract

The saturated vapour pressures of five heterocyclic compounds containing the pyridine fragment, namely, three isomers of aminopyridine (2-aminopyridine (2AmPy), 3-aminopyridine (3AmPy), and 4-aminopyridine (4AmPy)); 3-hydroxypyridine (3OHPy) and 2-(1H-imidazol-2-yl)pyridine (ImPy), were measured at appropriate temperature intervals using a transpiration (inert gas flow) method. The standard molar enthalpies, entropies, and Gibbs energies of sublimation for all the studied substances were determined. Among the compounds studied, the largest value of ΔH²⁹⁸_sub was observed for ImPy. The influence of substitution and the effects of hydrogen bonds in the crystal lattices on sublimation parameters are discussed herein. The reliable dependences relating ΔG²⁹⁸_sub to T_fus and ΔH²⁹⁸_sub to ΔG²⁹⁸_sub were plotted. A comparative analysis of several calculation schemes for the estimation of sublimation enthalpy and Gibbs free energy was carried out. Thermodynamic parameters obtained in this study were applied for the evaluation of cocrystallisation thermodynamic functions for two-component crystals (virtual screening) on the basis of the studied substituted pyridines.