Extended multidecker sandwich architecture of Cs+-18-crown-6 complexes stabilized in the environment of novel large iodocuprate(I) clusters obtained from zerovalent copper

The interaction of zerovalent copper with a proton-donating agent (NH4I) in acetonitrile solutions of CsX (X = Cl or I) and 18-crown-6 (18c6), in air, resulted in the formation of the novel mixed-metal complexes [Cs(18c6)(2)][Cu5I6(MeCN)(2)] 1, [Cs-2(18c6)(3)][Cu8I10(MeCN)(2)] 2 and [{Cs(18c6)}(6)Cu4I7][Cs-3(18c6)(3)][Cu7I10][Cu13I14]I-2 3. The main structural feature of the compounds is the multidecker sandwich Cs+-18c6 cations and finite iodocuprate(I) anions combined to form ionic lattices. It is proposed that the Cu+ oxidation state is stabilized in the presence of the Cs+-18c6 moieties in acetonitrile, and the overall formation of the solid phase is a template process of mutual stabilization of Cs+ as bulky [Cs-n(18c6)(m)](n+) cations and Cu+ as iodocuprate anions.