Herein we report on the synthesis, single crystal X-ray structure, spectroscopic and magnetic properties of [{Cu 2 (tidf)(H 2 O)} 2 (μ-CN) 2 Fe(CN) 4 ]·6H 2 O (1), [Cu 2 (tidf)(H 2 O) 2 ][Ni(CN) 4 ] (2) and [Cu 2 (tidf)(H 2 O) 2 ][Fe(CN) 5 NO]·H 2 O (3) (tidf=a Robson type macrocyclic ligand obtained on condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane). Complex (1) is pentanuclear; two paramagnetic dicopper(II) units are linked by a hexacyanoferrate(II) ion through two cyano-bridges. All compounds exhibit extensive, three-dimensional, supramolecular structures supported by classic hydrogen bonding between the coordinated aqua ligands, water molecules and cyano groups. Magnetism as a function of the temperature of complexes 1–3 is consistent with a strong antiferromagnetism with exchange parameters 2J estimated −783(29), −913(2), −905(1), respectively.