Crystal structures of the racemic 2-methyl-1-butanol and (S)-(−)-2-methyl-1-butanol solvates of the complex of 2,4,6-triethyl-1,3,5-benzenetricarboxylic acid·4,4′-bipyridine and the guest free form of this complex are reported. The solvates are isoskeletal and the host networks are centrosymmetric. On heating, the solvates are converted to the guest free form which shows similar two-dimensional hydrogen bonding topologies, with the two-dimensional layers interpenetrated.