Two new dialkyltin(IV) complexes of compositions [Me2Sn(LH)2(MeOH)] (1) and [nBu2Sn(LH)2(H2O)] (2) [LH– = 2-(2- (3,5-dimethyl-4-oxocyclohexa-2,5-dien-1-ylidene)hydrazinyl)benzoate] were prepared by the reactions of the carboxylate ligand (LHH) and Me2SnO or nBu2SnO in toluene solution followed by recrystallization from methanol/toluene. In the crystal structures of 1 and 2, the central tin atom is chelated by two carboxylate anions, a solvent molecule derived from the crystallization medium, and two alkyl groups, giving rise to a distorted pentagonal bipyramidal coordination. The phenol hydrogen atom has migrated to the nitrogen atom nearest the carboxylate group, thus leading to the quinoid form of the ligand. Extensive π···π interactions between the planar ligands, coupled with O–H···O, C–H···O, and C–H···π interactions complete three-dimensional supramolecular frameworks in each case. The solution properties were assessed from 1H, 13C, and 119Sn NMR spectroscopy.