The reaction of VO(SO4) with H8TBC [8] and NEt3 in refluxing MeOH, followed by crystallisation from MeCN, affords complex 13. The triply deprotonated H5TBC [8] ligand sits in a pleated-loop conformation, using two of its deprotonated O(Ph) atoms to bond to the single V V ion, whose tetrahedral geometry is completed by two terminal O 2-ions. The latter are H-bonded to the two HNEt3 cations that sit one above and one below the calix [8]arene plane. The third deprotonated O(Ph) atom lies directly opposite the {VO4} moiety, Hbonding to it two nearest neighbours.