Abstract The reaction of copper chloride dihydrate and ferric chloride hexahydrate with a tripodal N 4 ligand (ntb) under mild conditions affords two novel complexes [Cu(ntb)Cl] 2[CuCl 4] · 2H 2O ( 1) and [Fe(ntb)Cl 2]Cl · 3H 2O ( 2). The reaction of ferric chloride with another N 4 ligand, bispicpn, forms an octahedral mononuclear complex, [Fe(bispicpn)Cl 2]Cl ( 3). Single-crystal X-ray structural studies of 1, 2 and 3 reveal the formation of hydrogen-bond sustained 3D, 2D and 1D networks, respectively, involving (N–H⋯O) and (N–H⋯Cl) interactions. The packing arrangement in 2 further reveals the existence of hexagonal channels with helical propagation along the diagonal of the crystallographic b- and c-axes. The reactions of these complexes with 3,5-di- tert-butylcatechol have been studied in dimethylformamide. NMR techniques have been used to identify the reaction products.