Complexes [ SnII 3 (A--AsW9O34)2]12 (1) and [(PhSnIVOH)3(A--AsW9O34)2]12 (2) were synthesized by the reaction of tin(II) sulfate and phenyltintrichloride with A AsW9O9 34 in aqueous solution. Complex [(HOSnIVOH)3(AsW9O34)2]12 (3) is synthesized by the oxidation of 1 by Br2. The complexes were characterized by elemental analysis, IR, 119Sn NMR, UV–Vis spectroscopy, TGA, and single crystal analysis. The single crystal analysis was carried out on K12[Sn3(A--AsW9O34)2] 12H2O which crystallizes in the triclinic system, space group P-1 with a¼13.4503A ˚ , b¼20.393A ˚ , c¼28.898A ˚ , ¼87.376(2), ¼81.504(2), ¼86.335(3), V¼7818.2A ˚ 3, and Z¼4. Complex 1 consists of three SnII cations sandwiched between two AsW9O9 34 units. The coordination of each Sn is pseudo trigonal bipyramidal with the ‘‘equatorial’’ unshared electron pair directed toward the center of the anion. The 21 rotation of one AsW9O9 34 group with respect to the other AsW9O9 34 results in inequality of the equatorial (2.124A ˚ ) and axial (2.486A ˚ ) Sn–O bond lengths. The overall anion symmetry is D3. The 2 and 3 complexes display one-line 119Sn NMR corresponding to the three symmetry-equivalent Sn atoms.
