Synthesis, spectroscopic properties and crystal structure of organophosphoryl polyoxotungstate α-[Bu4N]3H[PhCH2P(O)]2SiW11O39

Reaction of the monovacant heteropolyanions alpha-[SiW11O39](8-) with PhCH2PO(OH)(2) leads to the formation of the organophosphoryl derivative alpha-[Bu4N](3)H[PhCH2P(O)](2)SiW11O39 ( 1). Single-crystal X-ray diffraction analysis shows that the crystal is monoclinic with space group P2(1)/n and the unit cell parameters: a = 14.386 (3) angstrom, b = 27.015 (5) angstrom, c = 25.480 (5) angstrom, alpha = 90 degrees, beta = 91.44 (3)degrees, gamma = 90 degrees, V = 9899 ( 3) angstrom(3). Z = 4, D-c = 2.467 g cm(-1), lambda (Mo- K alpha) = 0.071073 nm, R-1 = 0.0638, wR(2) = 0.1364. The hybrid anion consists of an alpha-[SiW11O39](8-) framework on which two equivalent organophosphoryl groups are grafted through P - O - W bridges; each of the two PhCH2P(O) groups are connected to two terminal oxygen atoms belonging to a triad and a diad, respectively.