Three new phenyltin-substituted polyoxometalates, ((CH3)2NH2)4[Sn(C6H5)PW11O39] (1), K7[Sn(C6H5)P2W17O61] (2), and ((CH3)2NH2)6K[Sn(C6H5)(H2O)P2W20O70(H2O)2] (3), have been synthesized and characterized by single crystal X-ray diffraction, 31P and 1H NMR, and FT-IR spectroscopy. Significantly, the mono-substituted phenyltin group in all three complexes is not positionally disordered. The Sn(C6H5) group is unambiguously determined and refined anisotropically with full occupancy, a result that is very unusual for mono-substituted polyoxometalates, and in particular polytungstates. Three factors account for these disorder-free mono-phenyltin-substituted polyanion structures: the steric bulk and rigidity of the phenyl group, hydrogen bonding and cation–π interactions between the phenyl ring and countercations. These results demonstrate the ability of a phenyl group to remove the crystallographically imposed positional disorder typically seen in mono-substituted polyoxometalates, an attribute that usually renders structural and structure-related reactivity studies of this large class of polyoxometalates quite difficult.
