Crystallization experiments of the wheel-and-axle host compound, 1,4-phenylene-bis(di-p-tolylmethanol), from pyridine and methylpyridine mixtures

Abstract

1,4-Phenylene-bis(di-p-tolylmethanol) (H), a host compound with the wheel-and-axle design, formed complexes with organic guest solvents pyridine (PYR) and 2-, 3- and 4-methylpyridine (2MP, 3MP and 4MP). The host: guest (H: G) ratios were 1:3, 1:2, 1:2 and 1:1, respectively. Host crystallization experiments from mixed guests demonstrated H to prefer both PYR and 4MP; however, it was established that these difficult-to-separate (by fractional distillations) guest mixtures cannot be purified/separated by means of H through supramolecular chemistry strategies owing to these selectivities for PYR and 4MP being less than optimal. Single crystal X-ray diffraction experiments showed that each guest compound was held in its complex by means of a classical hydrogen bond with H, and that one of the preferred guests, PYR, experienced a significantly shorter contact of this type than the other guests. Hirshfeld surface analyses demonstrated that PYR was also involved in a greater percentage of (guest)N···H(host) interactions compared with the other guest molecules. Thermal analyses, on the other hand, revealed that 4MP (also a favoured guest species) formed the most stable complex of the four in this investigation. These results with H were compared to those obtained when employing a closely related host compound from a previous report, 1,4-bis(diphenylhydroxymethyl)benzene: while both host species preferred the same guests (PYR and 4MP), the extent of the selectivity of that host compound compared with H in the present work was significantly more enhanced. Thus, minor modifications may deleteriously affect the selectivity behaviour of closely related host compounds.