Diverse and Yet Unified: A Comparative Study of the Supramolecular Assemblies of Three Diastereomeric Perhydro‐2,3,4a,6,7,8a‐naphthalenehexols

Self‐assemblies of three crystalline perhydro‐2,3,4a,6,7,8a‐naphthalenehexols 3 – 5 , all constructed on a trans ‐decalin framework, were compared with each other and to that of their diastereomeric all axial hydroxy sibling 2 , which was previously reported. The presence of the peripheral equatorial OH groups in 3 – 5 severs, to varying extents, the end‐to‐end intramolecular O–H ··· O hydrogen‐bonding chain linking the 1,3‐diaxial hydroxy groups on both faces of hexol 2 . Hence, the crystal packing in 3 – 5 deviates from the simple qualitative model proposed and observed in 2 . Though complex and seemingly individualistic upon a cursory glance, the supramolecular assemblies of all three hexols underscore two primary concepts of O–H ··· O hydrogen bonding, namely, maximization of the total number of hydrogen bonds per molecule and maximization of O–H ··· O hydrogen‐bond cooperativity by forming as many finite and infinite chains of hydrogen bonds as possible.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)