Unusual Caesium Monensinate A: Crystallographic Evidence for the Formation of Dinuclear Coordination Species in the Solid State.

The polyether ionophore monensin A (MonH), applied as silver monensinate, reacts with caesium cations to form a dinuclear complex [Mon2Cs2] the structure of which has been solved by single-crystal X-ray diffraction. Two Cs+ ions are located in the hydrophilic cage of two ligand anions, achieving coordination number eight. In addition, the metal cations are bridged by two functional groups of monensinate A, completing the inner tenfold coordination sphere. NMR studies show that the dinuclear complex dissociates to its mononuclear counterparts in methanol solutions. Further molecular dynamics theoretical modelling of the interaction of monensinate A with alkali metal ions reveals the effect of solvent polarity on the zipping ability of the ligand. Thus, in methanol, used as an explicit solvent, potassium and rubidium cations fully occupy the cavity of the ligand, whereas the sodium monensinate exists in an "open" form, with Na+ ions still interacting with the monodentate carboxylate group. The replacement of methanol by the less polar chloroform induces the folding of monensinate A and the formation of "closed" structures with all group 1 metal cations. The obtained data explain the specifics in the behaviour of monensinate A caused by the environment, e. g., physical state or solvent.