Hydrogen-Bonded Networks Based on Cobalt(II), Nickel(II), and Zinc(II) Complexes of N,N'-Diethylurea

N,N'-diethylurea (DEU) was employed as a ligand to form the octahedral complexes [M(DEU)(6)](2+) (M=Co, Ni and Zn). Compounds [Co(DEU)(6)](BF(4))(2) (1), [Co(DEU)(6)](CIO(4))(2) (2), [Ni(DEU)(6)](CIO(4))(2) (3), and [Zn(DMU)(6)](CIO(4))(2) (4) have been prepared from the reactions of DEU and the appropriate hydrated metal(II) salts in EtOH in the presence of 2,2-dimethoxypropane. Crystal structure determinations demonstrate the existence of [M(DEU)(6)](2+) cations and CIO(4) (-) (in 2-4) or BF(4) (-) (in 1) counterions. The [M(DEU)(6)](2+) cations in the solid state are stabilized by a pseudochelate effect due to the existence of six strong intracationic N-H cdots, three dots, centered O((DEU)) hydrogen bonds. The [M(DEU)(6)](2+) cations and counterions self-assemble to form hydrogen-bonded 2D architectures in 2-4 that conform to the kgd (kagome dual) network, and a 3D hydrogen-bonded rtl (rutile) network in 1. The nature of the resulting supramolecular structures is influenced by the nature of the counter-ion. The complexes were also characterized by vibrational spectroscopy (IR).