The synthesis of 1, characterized by a calix[4]arene backbone in 1,3-alternate conformation bearing four pyridines acting as hydrogen bond acceptors, was achieved and its solid state structure studied by X-ray diffraction on a single crystal; in the presence of 4,4′-biphenol 6 acting as a dihydrogen bond donor, compound 1 formed infinite single strand helical 1-D molecular networks which upon lateral association were packed in the crystalline phase as quintuple helices.