Silver(i) dithiocarboxylate complexes - clustering and aggregation

The neutral silver(i) dithiocarboxylate complexes silver(i) dithioacetate, silver(i) pentafluorodithiobenzoate, silver(i) 2,4,6-trimethyldithiobenzoate, silver(i) 2,4,6-tri-iso-propyldithiobenzoate and silver(i) 2,6-dimesityl-dithiobenzoate were synthesized and characterized by IR spectroscopy, elemental analyses and single crystal X-ray diffraction. All complexes form primarily dinuclear units with eight-membered rings [Ag2S4C2], which in turn aggregate by argentophilic interactions and additional AgS contacts in their crystal structures. The molecular structures and shapes of aggregation in the solid state are presented and discussed. The layer-like and chain-like aggregates as well as the [Ag] clusters formed are compared with the (almost) analogous gold(i) complexes.