Reactions of mixtures between Ag(NO 3 ) and alkaline earth nitrates with the bifunctional ligand 2,2′-{1,2-phenylenebis[oxyacetyl(N,N-diethylthiourea)]}, H 2 L cat , give {2}-metallacoronates of the composition {M ⊂ [Ag 2 (L cat ) 2 ]} (M = Ca 2+ , Sr 2+ , or Ba 2+ ). The trinuclear assemblies show further aggregation in the solid state, where they establish dimeric or polymeric entities stabilized by weak Ag···N (amide) interactions. Discrete {2}-[a]