The structures for Na+(12-crown-4)(2)SCN- and Na+(12-crown-4)(2)SCN-. HOMe have been determined by X-ray crystallography. In the crystalline solvate, the methanol molecule forms a nonaxial hydrogen bond to the nitrogen atom of thiocyanate anion. This uncommon hydrogen bonded structure markedly affects the frequency of the v(CN) vibration, which is lowered with respect to the unperturbed anion in Na+(12-crown-4)(2)SCN-. Theoretical studies of SCN-. HOMe complexes also predict that nonaxial hydrogen bonds lower the frequency of the v(CN) vibration, but potential energy calculations do not reveal the preferred angle for a nonlinear interaction.