The structure of a discrete hexacopper(II) barrel cluster and that of a coordination polymer formed by a related hexanuclear repeating unit have been determined. The Cu-II metals of the hexanuclear units are held together by eight chelating L-prolinato type ligands, which in turn provide the eight oxygen donors trapping a sodium ion in the center. The structure of the [Cu6Na] unit in the discrete system and in the infinite cluster-chain are essentially the same and both display intra-unit ferromagnetic superexchange. A preliminary magnetic study shows that, for both compounds, the copper centers within the [Cu-6] unit are ferromagnetically coupled, yielding an S = 3 spin ground state.
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