Cluster-Based Cu-II-Azide Polymers: Synthesis, Structure, Magnetic Properties, and Effect of Polyamines on Crystal Structures

Three new cluster-based Cull-azide coordination polymers, [Cu-8(N-3)(16)(222-tet)(2)](n) (1), [Cu-10(N-3)(20)(dien)(2)](n) (2), and [Cu-12(N-3)(24)(Me(5)dien)(2)](n) (3) as well as a 1D polymer [Cu-2(N-3)(4)-(dien)](n) (4) were prepared by hydrothermal reactions of Cull ions with NaN3 in the presence of various polyamines, Single-crystal X-ray diffraction studies reveal that 1 has a 1D chain structure based on an octanuclear cluster unit {Cu-8(N-3)(16)(222-tet)(2)}. Complexes 2 and 3 are 3D polymers and in both cases the azido anions display five different bridging modes (mu-1,1, mu-1,3, mu-1,1,1, mu-1,1,3, mu-1,1,1,3). Compound 4 is a 1D chain that represents the first example of a Cull-azide compound that contains cis-EE, double EO, and terminally bonded azido ligands. The magnetic susceptibility data, measured from 2 to 300 K, showed ferromagnetic couplings in 1, 2, and 4 and antiferromagnetic interaction in 3. The magnetic data of 1 and 4 were fitted v kith rough models, giving the exchange coupling constants J = 4.19 cm(-1) for I and J = 25.31 cm(-1) for 4.