C-13 and H-1 MAS NMR spectra of solid 1,8-bis(dimethylamino)naphthalene (DMAN) and several of its complexes have been measured. The presence of four resonances from quaternary carbons, six from protonated carbons, and four from methyl carbons demonstrates that the DMAN molecule is asymmetric. This is in agreement with the actual results from single-crystal X-ray diffraction but contrary to the accepted interpretation. In reality, the molecule is asymmetric as a result of interactions in the crystal. The estimated energies of intramolecular interactions permit the assignment of resonances from all 14 carbon atoms in the molecule. We discuss the role of protonation of DMAN in the redistribution of electron density.