Hexa-μ-acetato-chlorido­(μ-N,2-dioxodo­benzene-1-carboximidato)-μ(3)-oxido-tetra­iron(III)–water (1/1) and hexa-μ-acetato-(μ-N,2-dioxodo­benzene-1-carboximidato)fluorido-μ(3)-oxido-tri­pyridine­tetra­iron(III)–pyridine–water (1/1/0.24)

The title compounds, [Fe(4)(C(2)H(3)O(2))(6)(C(7)H(4)O(3))FO(C(5)H(5)N)(3)]·C(5)H(5)N·0.24H(2)O (1-F) and [Fe(4)(C(2)H(3)O(2))(6)(C(7)H(4)O(3))ClO(C(5)H(5)N)(3)]·H(2)O (1-Cl) were synthesized using a self-assembly reaction in methanol and pyridine with stoichiometric addition of salicyl­hydroxamic acid (H(3)shi), acetic acid (HOAc), and the appropriate ferric halide salt. The compounds crystallize as solvates, where 1-F has one pyridine mol­ecule that is disordered about a twofold axis and one water mol­ecule with an occupancy of 0.24 (2); and 1-Cl has one water mol­ecule that is disordered over two sites with occupancies of 0.71 (1) and 0.29 (1). The space groups for each analog differ as 1-F crystallizes in Fdd2 while 1-Cl crystallizes in P2(1). The difference in packing is due to changes in the inter­molecular inter­actions involving the different halides. The two mol­ecules are mostly isostructural, differing only by the torsion of the pyrine ligands and slight orientation changes in the acetate ligands. All of the iron(III) ions are in six-coordinate octa­hedral ligand field geometries but each one exhibits a unique coordination environment with various numbers of O (four to six) and N (nought to two) atom donors. Bond-valence sums confirm each iron is trivalent. The hydroximate ligand is bound to three iron(III) ions using a fused chelate motif similar to those in metallacrown compounds.