The two enantiomers of trans-1,2-diaminocylohexane form well-defined supramolecular structures with appropriately paired C-2 symmetrical 1,2-diols that are assembled by H-bonding. Depending on the structure and chirality of the diol, it is possible to form left- or right-handed trihelicate structures consisting of polar cores and hydrophobic outer residues. These structures can be sublimed without change, and they slowly adsorb carbon dioxide to eventually give polymeric amorphous fibers. Heating these materials regenerates the original 1:1 adducts as supramolecular entities. The patent diamines can be converted into crystalline carbamate salts which exist as layered trihelicate structures. Other charged supramolecular structures are formed from the (R,R)-diamine and the enantiomeric tartaric acids. The diamine molecule appears to be a superb assembler of neutral and charged supramolecular structures by accommodating preferred diol and acid partners in its crystal lattice. Molecular recognition and self-assembly are based on non-amidic H-bonding between amine and alcohol functions in the neutral molecules, leading to supramolecular structures whose helicity mode depends on the sense of chirality of the diamine used. All the reported structures were characterized by single-crystal X-ray analysis.