An investigation into the relationship between the asymmetric and symmetric stretching modes of ancillary carboxylate ligands and their mode of binding in a family of manganese(III) complexes of tetradentate N(2)O(2) Schiff base ligands, which includes comparison of an (18)O isotopically labelled derivative, has been undertaken. The results suggest that caution should be employed in using this technique to assign the binding mode of the carboxylate ligands in these complexes despite its very extensive use in the literature.