Molecular structure of the decamolybdodicobaltate(III) ion

When solutions of cobalt(II) ion and heptamolybdate ion (Mo₇O₂₄⁶⁻) are mixed in the presence of an oxidizing agent (such as bromine), Kurnakov, Hall, and others found that an emerald green complex is formed as the main product, namely, the heteropoly complex ion hexamolybdocobaltate(III), which forms salts such as (NH₄)₃[H₆CoMo₆O₂₄]·12H₂O. Friedheim and Keller showed that at the same time a small amount of another complex is also formed, having a Co:Mo ratio of 1:5. Tsigdinos, et al., found that if a hot solution of the hexamolybdocobaltate complex ion is treated with activated charcoal or Raney nickel the 1:6 complex is converted almost entirely to the 1:5 complex. These workers proved the latter to be a dimer, and formulated the ammonium salt (earlier prepared by Friedheim and Keller) as (NH₄)₆[Co₂Mo₁₀O₃₆]·10H₂O. We have now completed a crystal structure analysis of this interesting compound, which shows the proper formula to be (NH₄)₆[H₄Co₃Mo₁₀O₃₈]·7H₂O.