Synthesis, crystal structures and Hirshfeld analyses of phosphonothioamidates (EtO)(2)P(=O)C(=S)N(H)R (R = Cy, Bz) and their coordination on CuI and HgX2 (X = Br, I)

{The phosphonothioamidates (EtO)(2)P(=O)C(=S)N(H)R (L1 R = Cy; L2 R = Bz) have been prepared by nucleophilic addition of K[(EtO)(2)P(=O)] to R-N = C=S and crystallographically analyzed. Both compounds are associated pairwise through strong intermolecular N-H center dot center dot center dot O bonding giving rise to 10-membered supramolecular macrocycles. This intermolecular bonding has also been studied by Hirshfeld analysis of L1 and L2. Complexation of L on CuI in MeCN solution affords the dinuclear rhomboid-shaped thione complexes [{Cu(mu(2)-I)(2)Cu}(eta(1)-L)(2)] (1a,b). Crystallographic characterization of 1a reveals that L1 is ligated exclusively via the thione function to the trigonal Cu(I) centers, which are interconnected through a short Cu-Cu bond of 2.6207(4) angstrom. In the solid state, individual dimeric complexes are associated through intermolecular N-H center dot center dot center dot O bonding generating a supramolecular 1D ribbon. The dinuclear complexes [{XHg(mu(2)-X)(2)HgX}(eta(1)-L)(2)] (2a X = Br