A range of complexes based on the high-nuclearity {W36} isopolyoxotungstate cluster, [H12W36O120]12−, with a triangular topology has been isolated by using the organic cation, protonated triethanolamine. In analogy to an 18-crown-6 crown ether with six oxygen donors on a ring, the cluster can form alkali and alkaline earth metal complexes {M⊂W36} (M = K+, Rb+, Cs+, NH4+, Sr2+ and Ba2+, 1–6, respectively). Compounds 1–6 were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy. Comparisons between the structures of 1–6 and 18-crown-6 as well as the symmetry directing influence of the organo-cations in the isolation of the overall cluster architecture are discussed.
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