A new H-bonded supramolecular assembly of the diamine-diol family has been obtained from (1R,2R)-1,2-diaminocyclohexane (DAC) and (S)-1-phenyl-1,2-ethanediol (PED). The structure was characterized by single-crystal X-ray analysis and showed the typical architecture of DAC based assemblies, consisting of a three-stranded helicate coiling around a H-bonded core, with a predictable helicity sense determined by the configuration of DAC. The new assembly, while reconfirming the unique role of DAC as a powerful assembler of supramolecular structures, demonstrated that the C₂ symmetry of diol partners employed so far is not essential for assembling helicates, although chirality is. In the case of the adduct between (1R,2R)-1,2-diaminocyclohexane and (2R,3R)-2,3-butanediol, molecular recognition and self-assembly have been shown to take place even in the absence of solvent, in the gas phase, where long crystals were formed by spontaneous organized aggregation of diamine-diol units. A thorough analysis of the results from the present and previous investigations has lead to a deeper understanding of the key features of the diamine-diol molecular code and of the requirements for recognition and assembly.Key words: supramolecular, hydrogen bonding, molecular recognition, self-assembly, diamines, diols.