Supramolecular interactions in the structures of carboxylate derivatives of cymantrene and single-charged cations

The ability of cymantrenecarboxylate derivatives to form supramolecular structures has been studied for ten newly prepared derivatives of cymantrenecarboxylic acid (η5-C5H4COOH)Mn(CO)3 and two new derivatives of β-cymantrenoylpropionic acid (η5-C5H4CO(CH2)2COOH)Mn(CO)3 with cations of alkaline metals and protonated polytopic nitrogen bases of various geometries. It has been shown that structures of this kind (two- and three-dimensional) are formed owing to specific properties of the cymantrene moiety, i.e., its ability to coordinate metal ions via CO groups (to form isocarbonyl bridges) and to form CO⋯H hydrogen bonds, but in most of the cases the type of the structure is determined by the cation. In case of Li cymantrenecarboxylate complex the formation of hexameric molecules having a cavity was found. The crystal and molecular structure of cymantrenecarboxylic acid has been described for the first time.