Anion-controlled assembly of layer-type structures in double and triple salts of silver cyanide

Three new polymeric silver cyanide complexes AgCN·AgF·4AgCF3CO2·2CH3CH2CN (3), AgCN·AgCF3CF2CO2 (4) and AgCN·2AgCF3SO3·H2O (5) have been obtained by dissolving AgCN in an aqueous solution of AgX (X=CF3CO2, C2F5CO2 or CF3SO3) and AgBF4, and their layer-type crystal structures determined by X-ray crystallography. In the silver-rich environments, all the co-existing ancillary anions display unusual coordination modes: μ4-O,O,O′,O′-trifluoroacetate and pentafluoropropionate and μ4-η1κO:η1κO′:η1κ2O″-triflate. The cyanide ion functions as a μ3-η1κ2C:η1κN bridge in the construction of an unprecedented chain-like [Ag2(CN)]∞ motif in 4. [Copyright &y& Elsevier]