A series of 1-naphthylmethylammonium n-alkanoates from acetate to triacontanoate produce isomorphic layered structures in the crystalline state. The interlayer distances, d-spacings, are proportional to the lengths of the alkyl chains. This is attributed to synergic intermolecular interactions; pi-pi and CH-pi interactions of the naphthalene rings between the cations, hydrophobic interactions of the alkyl chains, and two-dimensional hydrogen-bond networks between the primary ammonium cations and the carboxylate anions. Salts made from carboxylic acids wider than 5.5 A in the cross sections produce another columnar structure with a one-dimensional ladder-type hydrogen-bond network. Steric parameters of the acid components provide an explanation for the isomerism of the hydrogen-bond network.