Synthèse et étude structurale d’un nouvel hétéropolytungstate substitué Na8〚H3XIIIMIIW17O59(H2O)〛·36 H2O (X = SbIII, BiIII et M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+) de structure identique à celle de 〚H2XIIIW18O60〛7– (X = As, Bi)

Abstract

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 〚H₃Sb^IIIM^IIW₁₇O₅₉(H₂O)〛^8– 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 〚H₂As^IIIW₁₈O₆₀〛^7–. There are two moieties Sb^IIIW₉O₃₀ and H₃M^IIW₈O₃₀. 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 〚H₃Bi^IIICu^IIW₁₇O₅₉(H₂O)〛^8–.