This tetramer possesses notable structural attributes, appearing as a potential contender to the conventional octahedral hexamer, given that each resorcinarene unit assumes a position at the vertices of a tetrahedron with water molecules intercalating the hydrogen bond network. However, its evident stability notwithstanding, this structure seems to be thermodynamically less preferable in contrast to other competing higher-order formations. Progressing to larger GI values we unceovered the presence of two hexameric structures, both characterized by somewhat disordered hydrogen bonding interactions with water molecules (D R and E R ). While these structures possess a degree of instability, their significance lies in their partial assembly, marking them as precursors to the ultimate assembly configuration. The culmination is the formation of state F R , where the hexamer, comprising exactly eight water molecules, takes shape, showcasing superior stability compared to its less ordered homologues. An observation of note is the autonomous positioning of water molecules, governed by a diffusive behavior operating on a distinctly faster timescale than the monomeric movements. From a thermodynamic perspective, for pyrogallolarene, the dominant equilibrium appears between isolated monomers and the hexamer. In contrast, for resorcinarenes, a balance is observed between the dimeric and hexameric states.