Crystal structures of N,N-dipicrylamine and its ionic complexes with N,N-di(2-pyridyl)amine, 1,8-bis(N,N-dimethylamino)naphthalene, 2,3-di(2-pyridyl)-6,7-dimethylquinoxaline, and 4-(dimethylamino)pyridine have been determined by single-crystal X-ray diffraction and infrared and solid-state NMR spectroscopies. in addition to intra- and intermolecular hydrogen bonds, all structures are stabilized by intra- and intermolecular N...O contacts resulting from electrostatic interactions between partially positively charged nitrogens and partially negatively charged oxygens in the nitro groups of symmetry-related molecules. Resonance structures of the nitro groups are used to rationalize these interactions. We consider the configuration of the oxygen atoms around the central nitrogen. Mesomerism of ionic structures and different types of hydrogen bonds are the main factors governing the 3D arrangement of dipicrylamine and its complexes. Principal structural features of the cations are discussed.