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Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C<jats:sub>1<\/jats:sub>C<jats:sub>1CN<\/jats:sub>Pyr)<jats:sub>2<\/jats:sub>(Tf<jats:sub>2<\/jats:sub>N)<jats:sub>4<\/jats:sub>] and [Co(C<jats:sub>1<\/jats:sub>C<jats:sub>2CN<\/jats:sub>Pyr)<jats:sub>6<\/jats:sub>][Tf<jats:sub>2<\/jats:sub>N]<jats:sub>8<\/jats:sub>, which were isolated from ionic\u2010liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. 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