The self-assembly between C2-symmetric (methanol)6 or S6-symmetric (ethanol)6 cyclohexamers and paddle-wheel dinuclear copper units leads to unique 1D polymer chains.

The first crystallographic evidences of the theoretically suggested C2-symmetric cyclohexameric form of liquid methanol and the S6-symmetric cyclohexameric form of liquid ethanol are reported, trapped inside a hydrophilic pocket shielded by tert-butyl groups.