Two new oxo complexes, namely hexa-μ₂-acetato-acetatoaquabis(di-3-pyridylamine)di-μ₃-oxo-tetrairon(III) chloride monohydrate ethanol 1.25-solvate, [Fe₄(C₂H₃O₂)₇O₂(C₁₀H₉N₃)₂(H₂O)]Cl·1.25C₂H₆O·H₂O, (I), containing a tetranuclear [Fe₄(μ₃-O)₂]⁸⁺ unit, and 2-methylimidazolium hexa-μ₂-acetato-acetatodiaqua-μ₃-oxo-triiron(III) chloride dihydrate, (C₄H₇N₂)[Fe₃(C₂H₃O₂)₇O(H₂O)₂]Cl·2H₂O, (II), with a trinuclear [Fe₃(μ₃-O)]⁷⁺ unit, are presented. Both structures are formed by two well differentiated entities, viz. a compact isolated cluster composed of Fe^III ions coordinated to O^2- and CH₃CO₂^- anions, and an external group formed by a central Cl^- ion surrounded by different solvent groups to which the anion is bound through hydrogen bonding. In the case of (I), charge balance cannot be achieved within the groups, so the structure is macroscopically ionic; in the case of (II), in contrast, each group is locally neutral owing to the internal compensation of charges. The trinuclear complex crystallizes with the metal cluster, chloride anion and 2-methylimidazolium cation bisected by a crystallographic mirror plane.