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 within 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.