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

Abstract

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, [Cs₂(18c6)₃][Cu₈I₁₀(MeCN)₂] 2 and [{Cs(18c6)}₆Cu₄I₇][Cs₃(18c6)₃][Cu₇I₁₀][Cu₁₃I₁₄]I₂ 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.