Lead(<scp>ii</scp>) supramolecular structures formed through a cooperative influence of the hydrazinecarbothioamide derived and ancillary ligands

In this work we report on new heteroleptic coordination compounds [Pb2(LI)2](NO3)2∙2MeOH (1), [Pb2(LII)2](NO3)2 (2), [Pb2(LIII)2](NO3)2∙MeOH∙H2O (3) and [Pb2(LIII)2(H2O)](NCS)2 (4), which were obtained through self-assembling of 2-(amino(pyridin-2-yl)methylene)hydrazine-1-carbothioamide (HLI), 2-(amino(pyrazin-2-yl)methylene)hydrazine-1-carbothioamide (HLII) or 2-(amino(pyridin-2-yl)methylene)-N-methylhydrazine-1-carbothioamide (HLIII) with Pb(NO3)2 or a mixture of Pb(ClO4)2 and KNCS, respectively. In all the obtained complexes the lead(II) cation is N,N&#39;,S-chelated by the tridentate pincer type monodeprotonated ligand LI–III. In addition to the thiosemicarbazone chelation, the sulfur atom in each structure acts as bridging to connect two [Pb(LI–III)]+ units to form a dinuclear dimeric species having a centrosymmetric geometry, so that the ligands are directed either at different, in 1 and 2, or the same, in 3 and 4, side of the coplanar Pb2S2 core. In the latter structures two metal centers are additionally linked with each other through the oxygen atom of the bridging water molecule. The dimeric units in 1–4 are further linked through the Pb–N tetrel bonds, yielding 1D supramolecular polymeric chains, which, in turn, are interlinked though a myriad of other intermolecular noncovalent inetaractions, including tetrel bonds, hydrogen bonds and π-stacking. Counterions (NO3– and NCS–) as well as co-crystallized solvent molecules (MeOH and H2O) are also responsible in further stabilization of the overall crystal packing of the obtained complexes as a source of either tetrel and/or hydrogen bonds. The observation of the recurrent tetrel bonds in compounds 1–4 has been rationalized using DFT calculations and molecular electrostatic potential (MEP) surface plots. Moreover, coordination bonds (covalent character) and tetrel bonds (noncovalent character) between the complexes and their conterions (and water moelcule) have been differentiated using the quantum theory of &#171;atoms-in-molecules&#187; (QTAIM) and the noncovalent interaction index (NCI index) computational methods.