Diverse and yet unified: a comparative study of the supramolecular assemblies of three diastereomeric perhydro-2,3,4a,6,7,8a-naphthalenehexols

Abstract

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.