Investigation of structure-directing interactions within copper(i)thiocyanate complexes through X-ray analyses and non-covalent interaction (NCI) theoretical approach

Herein, we reported the synthesis of copper?I) thiocyanate complexes with ortho-pyridinyl carbohydrazones containing a thiophene (L1) or a furyl ring (L2) as a mixture of two different crystals for each compound, linkage isomers of C1N, [Cu?NCS)?L1)PPh3] and C1S, [Cu(SCN)(L1)PPh3], for L1, whereas monomeric and polymeric structures C2N, [Cu(NCS)(L2)PPh3], and C2P, [–(NCS)Cu(L2)–]n, for L2. Crystallographic information and theoretical calculations, mainly noncovalent interaction reduced density gradient (NCI-RDG) analyses, were pursued to generate a profound understanding of the structure-directing interactions in these complexes. The supramolecular assemblies are first driven by cooperative p?p interactions and hydrogen bonds followed by CH?p, S?S and S?p linkages. In the case of the linkage isomers, intermolecular interactions may have a significant role in the formation of the less stable S-bound isomer C1S.