Supramolecular cations of (m-halogenated-anilinium)(dibenzocrown-6) in Keggin [SMo12O402−] polyoxometallates†
Four supramolecular cations (m-XAni+)(DBcrown-6) (X = F, Cl, Br or I; Ani+ = anilinium ion; DBcrown-6 = dibenzocrown-6) were introduced into crystals of a Keggin [SMo12O402−] polyanion to form [(m-XAni+)(DBcrown-6)]2[SMo12O402−]·4CH3CN (1, 2, 3 or 4 for X = F, Cl, Br or I) through a hydrogen-bonding interaction. Crystals 1, 2, 3 and 4, which were isomorphous to each other, crystallized in the monoclinic space group P21/n. Supramolecular cations (m-XAni+)(DBcrown-6) were constructed by a N–H+⋯O hydrogen-bonding interaction. [SMo12O402−] polyoxoanions were infinitely extended in three dimensions through a weak C–H⋯O hydrogen-bonding interaction with DBcrown-6. Disorder of the halogen atoms at the meta-position was observed in crystals 1, 2 and 3. The rotational freedom of the (m-XAni+) cations was suppressed because of weak interactions with surrounding molecules.