Abstract
Isostructural relations and phase transitions of dihalomethanes have been rationalized by the competing patterns of CH...halogen hydrogen bonds and halogen...halogen interactions, the common weak directional interactions in soft organic matter. Pressure-frozen chloroiodomethane, CH(2)ClI, at 295 K and 0.72 GPa forms centrosymmetric phase III, which at ca. 400 K and 1.6 GPa disproportionates into CH(2)Cl(2) and CH(2)I(2). The directional character of intermolecular contacts between halogen atoms results from the characteristic anisotropic charge distribution on molecular surface.
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