Synthesis and structural study of a novel substituted heteropolytungstate Na8[H3XIIIMIIW17O59(H2O)]•36 H2O (X = SbIII, BiIII, and M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+) with a structure identical to this of [H2XIIIW18O60]7- (X = As, Bi).

By mixing an aqueous solution of antimonotungstate at pH = 4-5 and an aqueous solution of manganese(II) chloride, of cobalt(II) chloride, of nickel(II) chloride, or of zinc, a monosubstituted heteropolytungstate [(H3SbMW17O59)-M-III-W-II(H2O)](R-) is obtained (M-II = Mn-II, Co-II, Ni-II, Zn-II). The crystallographic study, associated to EPR, XANES, EXAFS, and proton NMR spectrometries, leads to a structure identical to this of [(H2AsW18O60)-W-III](7-). There are two moieties (SbW9O30)-W-III and (H3MW8O30)-W-II. It is concluded that the M-II atom substitutes a tungsten atom of the belt of six octahedra perpendicular to the ternary axis of the polytungstate, The same type of compound was obtained starting from bismuth chloride and copper acetate, that is [(H3BiCUW17O59)-C-III-W-II(H2O)](8-). (C) 2001 Academie des sciences / Editions scientifiques et medicales Elsevier SAS.