Low-temperature phase transition and high-pressure phase stability of 1H-pyrazole-1-carboxamidine nitrate

Abstract

The phase transition observed in a temperature-dependent experiment at 174 K is unachievable under high-pressure conditions. Negative thermal expansion for phase (II) and negative compressibility for phase (I) were observed. A new salt of 1H-pyrazole-1-carboxamidine, (HPyCA)NO3, for guanylation reaction was obtained in a crystalline form. The compound crystallizes in monoclinic space group P21/c and a phase transition at 174 K to triclinic modification P 1 was found. An unusual increase of the unit-cell volume was observed just after transition. Although the volume decreases upon cooling, it remains higher down to 160 K in comparison to the unit-cell volume of phase (I). The mechanism of the phase transition is connected with a minor movement of the nitrate anions. The triclinic phase was unreachable at room-temperature high-pressure conditions up to 1.27 GPa. On further compression, delamination of the crystal was observed. Phase (I) exhibits negative linear compressibility, whereas abnormal behaviour of the b unit-cell parameter upon cooling was observed, indicating negative thermal linear expansion. The unusual nature of the compound is associated with the two-dimensional hydrogen-bonding network, which is less susceptible to deformation than stacking interactions connecting the layers of hydrogen bonds. Infrared spectroscopy and differential scanning calorimetry measurements were used to investigate the changes of intermolecular interactions during the phase transition.