Piperidine and 1,1,1-3,3,3 hexafluoro-2-propanol (HFIP) were co-crystallized and x-ray crystal structure was explored. Single-crystal x-ray anal. displays the existence of hydrogen bonding aggregates through dimers 1 of (one piperidine/two HFIP) where the heteroatoms form a six-center ring. In this cluster 1, each heteroatom (N, O) is multiple H-bond donor and acceptor. Surprisingly the strongest H-bond of the network is where HFIP acts as an acceptor from the amine. In this complex HFIP adopts a conformation different from that of HFIP aggregates. The supramol. architecture is also based on discrimination between polar and hydrophobic parts that allows the alignment of mols. and the formation of parallel channels. NMR experiments show that strong interactions between piperidine and HFIP are maintained in solution