AgI Metallacoronates and HgII Metallacryptates Derived from a Catechol‐Based Aroylbis(N,N‐diethylthiourea)

Reactions of mixtures between Ag(NO3) and alkaline earth nitrates with the bifunctional ligand 2,2′‐{1,2‐phenylenebis[oxyacetyl(N,N‐diethylthiourea)]}, H2Lcat, give {2}‐metallacoronates of the composition {M ⊂ [Ag2(Lcat)2]} (M = Ca2+, Sr2+, or Ba2+). 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}‐metallacryptate species {M ⊂ [Hg2(Lcat)3]} (M = Sr2+ or Ba2+) result from similar reactions between H2Lcat, Hg(NO3)2, and strontium nitrate or barium nitrate. The complexes contain HgII ions in an uncommon distorted trigonal‐bipyramidal environment with a S3O2 coordination sphere. The central alkaline earth ions are mainly bonded by the six carbonyl oxygen atoms of the three organic ligands.