The Effect of High Pressure on Polymorphs of a Derivative of Blatter’s Radical: Identification of the Structural Signatures of Subtle Phase Transitions

The effect of pressure
on the α and β polymorphs
of
a derivative of Blatter’s radical, 3-phenyl-1-(pyrid-2-yl)-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl, has been investigated using single-crystal
X-ray diffraction to maximum pressures of 5.76 and 7.42 GPa, respectively.
The most compressible crystallographic direction in both structures
lies parallel to π-stacking interactions, which semiempirical
Pixel calculations indicate are also the strongest interactions present.
The mechanism of compression in perpendicular directions is determined
by void distributions. Discontinuities in the vibrational frequencies
observed in Raman spectra measured between ambient pressure and ∼5.5
GPa show that both polymorphs undergo phase transitions, the α
phase at 0.8 GPa and the β phase at 2.1 GPa. The structural
signatures of the transitions, which signal the onset of compression
of initially more rigid intermolecular contacts, were identified from
the trends in the occupied and unoccupied volumes of the unit cell
with pressure and in the case of the β phase by deviations from
an ideal model of compression defined by Birch–Murnaghan equations
of state.