The structure of the simplest stibatrane has been a mystery since it was first prepared in 1966. This study reports the preparation and characterization of two stibatranes from triethanolamine and triisopropanolamine. Solid state structures reveal macrocycles that contain favourable inter- and intramolecular pnictogen bonds. Solution studies, corroborated by DFT analysis, reveal an equilibrium mixture assigned to monomer and pnictogen-bonded dimer. This allowed for the determination of an enthalpy associated with pnictogen bond formation of -27 kJ mol-1, in line with the supramolecular nature of these interactions.