Crown Thioether Complexes of AgI and CuI: The Crystal Structures of [{Ag3L3}AgL{AgL2}](ClO4)4 and [LCuI] (L = 1, 4, 7‐Trithiacyclononane)

A crown thioether molecule as bridging ligand and two types of cations in the molecule are the most striking features of the silver complex [Ag4L5](ClO4)4 (L = 1,4,7‐trithiacyclononane). In the cation [AgL2]⊕, Ag⊕ is surrounded by six S atoms, in the cation [Ag3L3]3⊕ by four. One S atom of each of the three ligands in [AgL,]3⊕ is bound to two Ag⊕. In contrast, the soft Lewis base I⊕ in [LCuI] competes with the S atoms for coordination positions. In the resulting monomeric units, Cu⊕ is coordinated in a distorted tetrahedral fashion by three S atoms and one I⊕.