The complexation of carboxylic acid Monensin A (MonH, 1a) with CoCl2.6H2O and MnCl2.4H2O leads to the formation of mononuclear complexes [Co(Mon)2(H2O)2], 2a and [Mn(Mon)2(H2O)2], 2b, respectively. The unique crystal structures of 2a and 2b were determined by X-ray crystallography. The complexes crystallize in the monoclinic space group P2 1 with an octahedrally coordinated transition metal center forming the crystallographically centrosymmetric chromophore CoO6 or MnO6, respectively. Two molecules of Monensin A act bidentately through their carboxylate moiety and a hydroxyl group, and two water molecules are additionally trans-coordinated. Although the transition metal ions are not bound into the cavity of the ligand, the unusual bidentate coordination mode of the ionophore induces its "pseudo-cyclization" forming 22-membered cycles further stabilized by a number of H-bonds. The complexes are the first example of divalent metal complexes of the monovalent polyether ionophore. The parallel study on the complexation ability of the potassium complex of Monensin A (MonK, 1b) towards Co(II) and Mn(II) showed the formation of the isostructural complexes 2a and 2b accompanied by loss of the potassium ion due to the new coordination mode of the ligand. The biological tests performed with the antibiotic MonH and the corresponding metal(II) complexes show greatly enhanced antimicrobial activity of complexes 2a-b against Gram(+)-bacteria.

Alkaline-earth metal complexes of the monoanionic form of the polyether ionophore monensin A were isolated for the first time in solid state and were structurally characterized using various spectroscopic methods (IR, NMR, FAB-MS). The stoichiometric reaction of monensic acid (MonH) with M(2+) (M = Mg, Ca) in the presence of an organic base leads to the formation of mononuclear complexes of composition [M(Mon)(2)(H(2)O)(2)]. The structures of magnesium (1) and calcium (2) monensin complexes in the solid state were established by single crystal X-ray crystallography. The complexes crystallize as [Mg(Mon)(2)(H(2)O)(2)]x5MeCN (1) and [Ca(Mon)(2)(H(2)O)(2)]xH(2)Ox5MeCN (2) in the monoclinic P21 space group. The alkaline-earth metal ion is placed in a distorted octahedral environment, defined by two monensin anions acting as bidentate ligands in the equatorial plane of the complex as well as by two water molecules occupying the axial positions of the inner coordination sphere. The bactericidal activity of 1 and 2 was evaluated against aerobic Gram-positive microorganisms applying the double layer agar hole diffusion method.

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Cobalt (Co)

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In the present paper the synthesis and structural characterization of alkaline-earth metal(II) complexes of the polyether ionophorous antibiotic salinomycinic acid (SalH.H2O) are discussed. The complexes [M(Sal)2(H2O)2] (M = Mg2+, 1; Ca2+, 2; Sr2+, 3; Ba2+, 4) were obtained reacting salinomycinic acid and Et4NOH with the corresponding metal(II) salts at metal-to-ligand-to-base molar ratio of 1:1:1. The spectral properties of 1–4 were characterized using infrared spectroscopy, fast atom bombardment-mass spectrometry, nuclear magnetic resonance and elemental analysis data. The crystallinity degree and morphology of complex 2 were studied by X-ray powder diffraction and transmission electron microscopy. The biometal(II) salinomycinate complexes 1 and 2 possess an enhanced antimicrobial activity compared to the parent antibiotic against Gram-positive bacteria. The comparison between the effectiveness of the complexes, reported here, and the already known isostructural coordination species of salinomycin and monensin (MonH.H2O), revealed that magnesium(II) and calcium(II) monensinates appear to be promising antibacterial agents against Bacillus subtilis, Bacillus cereus and Micrococcus luteus.