Identification of seven-coordinate LnIII ions in a LnIII[15-MCFe III N(shi)-5](OAc)2Cl species crystallized from methanol and pyridine.

The title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2CI(C5H5N)6 (Ln1), where OAc- is acetate, shi3- is salicylhydroximate, and Ln = Gd and Dy, were synthesized via a self-assembly reaction in methanol and pyridine. Single crystals were grown using slow evaporation and characterized using X-ray diffraction. Seven-coordinate capped octahedron geometries were observed for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species. The 15-MC-5 is a ruffled metallacrown archetype similar to previously reported mixed-valent manganese metallacrowns.