Melting point-structure relationships of multicomponent crystals

Abstract

Twelve multicomponent crystals of dicarboxylic acids (succinic, adipic and suberic acid) with derivatives of picoline (4-picoline, 2,4-lutidine, 3,4-lutidine and 3,5-lutidine) were analyzed with the aim of finding correlation between their melting points and crystalline structural features. The solvates of SUC•2,4LUT, SUC•3,4LUT, SUC•3,5LUT and ADP•4PIC are already known structures but were remade for completeness and to obtain their accurate melting temperatures. The acids were selected because of their systematically increasing chain lengths and the selection of the picoline derivatives were based on the systematic variation of the positions of the methyl groups around the pyridine moiety. All the formed multicomponent crystals were analyzed with single crystal X-ray diffraction and parallel to the solution crystallizations, grinding experiments were carried out to prepare the aimed inclusion compounds by using much less of the solvent of crystallization. Thermogravimetry was used to confirm the solvent content of the bulk material and differential scanning calorimetry was applied to obtain information about the melting process, such as the onset and the peak temperature of the melting and the concomitant enthalpy change. The melting temperatures revealed that the inclusion formation significantly decreased the melting points of the staring materials and the melting points of the inclusion compounds for the same acid varied significantly. Hirshfeld surfaces of the base-acid-base moieties and the related fingerprint plots were compared both qualitatively and quantitatively. The melting points of the compounds were plotted against the percentage contribution of the various intermolecular interactions.