Structural, kinetic and thermodynamic aspects of the conformational dimorphism of diethyl 3,6-dibromo-2,5-dihydroxyterephthalate

Abstract

The crystal structures of the title compound and of its ethanol solvate have been determined by X-ray diffraction. The compound crystallizes in two different crystal forms (I: P21/n, high-temperature stable modification, II: P21/c, room-temperature stable modification), which differ in molecular conformation and hydrogen bonding. Ab initio calculations show that both observed conformations correspond to local energy minima and predict the conformation in polymorph (II) to be energetically more favourable. Packing energy calculations confirm that form (II) should be more stable than form (I). Crystals of both modifications and a solvate, containing 2 equiv, of ethanol, can be obtained by slow crystallization from ethanolic solution. Modification (II) transforms to (I) at 391 K, as shown by optical microscopy, powder diffraction and differential thermal analysis (DTA), whereas (I) melts at 429 K without previous transformation.