Molecular interactions in crystalline dibromomethane and diiodomethane, and the stabilities of their high-pressure and low-temperature phases.

Dibromomethane, CH2Br2, and diiodomethane, CH2I2, have been in situ pressure-crystallized in a diamond-anvil cell and their structures determined by single-crystal X-ray diffraction at 0.61 and 0.16 GPa, respectively. The pressure-frozen CH2Br2 crystal is isostructural with its C2/c phase obtained by cooling. CH2I2 is known to form several phases at low temperature, one of which is isostructural with CH2Br2. However, pressure freezing leads to the polar Fmm2 phase. The formation of the polar CH2I2 structure at 0.16 GPa has been rationalized by the electrostatic and anisotropic van der Waals interactions of the I atoms. No ferroelectric behaviour of the Fmm2 polar phase II of CH2I2 has been determined. The diffraction, calorimetric and dielectric constant studies reveal considerable temperature hysteresis of transformations between the CH2I2 phases, as well as metastable regions strongly dependent on the sample shape and history.