Phase transitions in hydrogen-bonded phenol–amine adducts: analysis by ferroelastic theory

Phase transitions in a recently discovered class of hydrogen-bonded organic crystals are analyzed by Landau theory. It is shown that the transitions are ferroelastic. Two types of transition, orthorhombic-to-monoclinic and monoclinic-to-triclinic, are analysed using an expansion of the free energy in symmetry-allowed powers of the strain components. For three examples, new data are presented for the crystallographic parameters in a range of temperature including the phase transition point Tc. These data show that the transitions are second order and the temperature dependences are consistent with the mean-field analysis. We propose that the making and breaking of the hydrogen bond interactions with variation of temperature accounts for these reversible ferroelastic phase transitions. Expressions are derived for the entropy and the specific-heat discontinuity at Tc. It is pointed out that the transitions should be accompanied by ‘soft-mode’ behavior in a phonon of appropriate symmetry.