Organotin derivatives of alpha-[XIIIW9O33]9- (X = As,Sb) heteropolytungstates. Solution- and solid-state characterization of [[C6H5Sn)2O]2H(alpha-AsW9O33)2]9- and [(C6H5Sn)3Na3(alpha-SbW9O33)2]6-

The tris(phenyltin)-substituted tungstoantimonate(III) Cs6(PhSn)3Na3(alpha-SbW9O33)2].20H2O (1) and the tetrakis-(phenyltin)-substituted tungstoarsenate(III) Na9(PhSn)2O]2H(alpha-AsW9O33)2].20H2O (2) have been prepared by reaction of phenyltin trichloride with Na9alpha-SbW9O33].19.5H2O and Na9alpha-AsW9O33].19.5H2O, respectively, in aqueous solution. The products were characterized by elemental analysis, X-ray crystallography, multinuclear NMR, and infrared spectroscopy. Crystals of 1 are monoclinic, space group P2(1)/n, with a = 13.7952(1) A, b = 22.3133(2) A, c = 34.4493(2) A, beta = 90.933(1) degrees, and Z = 4. Anion 1 has nominal D3h symmetry and contains three PhSn3+ groups and three sodium ions sandwiched between alpha-SbW9O33]9- units. Crystals of 2 are triclinic, space group P1, with a = 15.272(6) A, b = 15.303(6) A, c = 16.760(7) A, alpha = 93.59(3) degrees, beta = 106.187(19) degrees, gamma = 112.23(3) degrees, and Z = 1. Anion 2 has nominal C2h symmetry and contains four PhSn3+ groups sandwiched between two alpha-AsW9O33]9- units.