Novel quaternary n-dodecyldimethylammonium picrates with two to four chains connected by an ethylene spacer at the ammonium headgroup level were synthesized. The effect of the headgroup number and the impact of picrate anion to their physicochemical properties was examined. A crystal structure of dimeric dipicrate is significantly different from bromide analogue. The dominant feature of this crystal packing is a layered structure with aromatic rings of picrate molecules, stacked via strong pi...pi interactions and connected to the alkylammonium molecules with their nitro groups by C-H center dot center dot center dot O hydrogen bonds. Weak NO2 center dot center dot center dot HC hydrogen bonds further stabilize the structure. Higher degree of oligomerization leads to the less-ordered solid phase and amorphous picrate structure. These amorphous structures result from widespread and disordered hydrogen bonding and rupture of pi...pi stacking in samples with more than two headgroups. Unlike corresponding bromides, picrate compounds show reversible phase transitions without thermal decomposition. Temperature-dependent infrared spectroscopy in the liquid phase detected adiabatic phase transitions. (C) 2013 Elsevier B.V. All rights reserved.