The synthesis, crystal structure and magnetic properties of the cyano-bridged complex [{Cu(cyclam)} 3 {Fe(CN) 6 } 2 ]·6H 2 O are reported. Its structure is made up of centrosymmetric S-shaped pentanuclear [{Cu(cyclam} 3 {Fe(CN) 6 )} 2 ] units, in which three [Cu(cyclam)] 2+ units are alternatively bridged by two trans-CN groups of [Fe(CN) 6 ] 3− anions and water molecules. The pentanuclear Fe 2 Cu 3 units are held together by two complementary and very weak Fe–CN⋯Cu1 bonds, forming a rope-ladder chain along the c axis. The compound exhibits a ferromagnetic interaction between the Cu(II) and Fe(III) ions as a consequence of the orthogonality of their magnetic orbitals of σ and π nature, respectively. The magnetic data were fitted to the calculated magnetic susceptibility equation for a pentanuclear model, leading to the following magnetic parameters: J 1 =9.0(3)cm −1 , J 2 =3.8(4)cm −1 , g=2.2, θ=−1.2K. These results show that the interactions through the long Cu–N axial bonds are not so weak as is usually assumed.