Networking of macrocycles: 1D and 2D coordination polymers of dithia-18-crown-6 with copper(ii) and copper(i)

CuI and CuII coordination polymers of 1,10-dithia-18-crown-6 (L) with unusual networking modes involving an exocyclic coordination are presented. The reaction of L with copper(II) nitrate gave a unprecedented ladder-type 1D coordination polymer {[(LOXOX)Cu2(NO3)2(H2O)4](LOXOX)(NO3)2·2H2O}n (1) via strong CuII–Osulfoxide bonds because L was oxidized to the disulfoxide macrocycle (LOXOX) under the present conditions. Meanwhile the parallel reaction of copper(I) iodide with L in the presence of cobalt(II) perchlorate yielded a mixture of an emissive 2D network product [(Cu4I4)(L)2]n (2) linked with cubane-type Cu4I4 clusters and a non-emissive 1D coordination polymer {[(Cu2I2)(L)2][Co(H2O)6](ClO4)2·0.5H2O}n (3) linked with rhomboidal Cu2I2 cores. In 3, hexaaquacobalt(II) complexes, anions and water molecules also exist and stabilize the 1D macrocyclic network through H-bonds.