Hydrogen-Bonding Networks of Adamantane-Based Bisphenol Molecules: Toward the Preparation of Molecular Crystals with Channels

A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual molecules in crystalline lattices. Single crystal X-ray analysis revealed that multiple intermolecular hydrogen bonds were formed between the hydroxyl groups of the phenol moieties. Crystallographic analysis of 1,3-bis(4-hydroxy-3,5-dimethylphenyl)adamantane (1) indicated the creation of a one-dimensional (1D) zigzag polymer through hydrogen bonds. In the crystals of 1,3-bis(3-bromo-4-hydroxyphenyl)adamantane (2), infinite 1D polymers composed of cyclic frameworks were sustained by intermolecular hydrogen bonds. 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3) and 1,3-bis(4-hydroxyphenyl)adamantane (4) formed frameworks with channels containing chloroform molecules in the solid state. Continuous 1D polymers consisting of cyclic frameworks were generated in crystals 3a and 4a, and these 1D polymers packed into two-dimensional (2D) layers with channel structures.