Chains and nanochannels self-assembled from carbido clusters, silver ions and heterocyclic ligands-Crystal structures of the 1D coordination polymers [{AgOC4H8[Rh6C(CO)15]-AgOC4H8}pyz]_infinite and [bipy{Ag2Ru6C(CO)16}(bipy)2{Ag2Ru6C(CO)16}●2 C4H8O]_infinite

Two prototypical carbido anionic clusters, the prismatic [Rh6C(CO)15]2– and the octahedral [Ru6C(CO)16]2–, can add two electrophilic Ag–NCMe+ fragments, which were exploited to condense the clusters with bifunctional heterocyclic ligands, such as pyrazine (pyz) or 4,4 -bipyridine (bipy), forming 1D chains of formula [{Ag(OC4H8){Rh6C(CO)15}Ag(OC4H8)}pyz] and [bipy{Ag2Ru6C(CO)16}(bipy)2{Ag2Ru6- C(CO)16}·2C4H8O], both characterized by single-crystal X ray diffraction. In the former, the two Ag+ ions are on opposite sides, and the chains are tightly packed. In the latter, the two silver ions are directly bound, and the metal clusters are connected alternatively by one and two linkers, giving rise to large channels.