Copper and silver triimidosulfites:: S(NtBu)32--bicapped M3-triangles connected via lithium halide ladders or fragments thereof

Starting from the dilithium triimidosulfite dimer [Li-4{((NBu)-Bu-t)(3)S}2], only three of the four lithium cations can be replaced by copper(I) cations in [(thf)(2)Cu3Li2I{((NBu)-Bu-t)(3)S}(2)] (1). In the isomorphous silver complex [(thf)(2)Ag3Li2Br{((NBu)-Bu-t)(3)S}(2)] (2), the cations are arranged in a triangle. Each metal is linearly coordinated by two imido nitrogen atoms, resulting in relatively short Cu...Cu (251.41 pm) and Ag...Ag (278.60 pm) distances. Two lithium cations are additionally coordinated to each S((NBu)-Bu-t)(3)(2-) cap. They pincer a single halide anion. [(thf)Ag3Li2Br{((NBu)-Bu-t)(3)S}(2)](2) (3) and [(thf)(2)Ag3Li3Br2{((NBu)-Bu-t)(3)S}(2)](2) (4) show an increasing content of lithium bromide. In 3 a two-rung and in 4 a four-rung LiBr ladder is terminated by a LiM3{((NBu)-Bu-t)(3)S}(2) unit. In [(thf)(2)Li3Cl{((NBu)-Bu-t)(3)S}](2) (5), no LiCl ladder extension is observed presumably because the Li-2((NBu)-Bu-t)(3)S terminating moiety meets the requirements of the cubic LiCl solid-state lattice.