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The title compound, [Fe(C 3 H 7 NO) 6 ][Cd 2 Cl 7 ], crystallizes in the trigonal space group R and is assembled from discrete [Fe(DMF) 6 ] 3+ cations (DMF = N , N -di-methyl-formamide) and [Cd 2 Cl 7 ] 3- anions. In the cation, the iron(III) atom, located on a special position of site symmetry, is coordinated by six oxygen atoms from DMF ligands with all Fe-O distances being equal [2.0072 (16) Å]. A slight distortion of the octa-hedral environment of the metal comes from the cis O-Fe-O angles deviating from the ideal value of 90° [86.85 (7) and 93.16 (7)°] whilst all the trans angles are strictly 180°. The central Cl atom of the [Cd 2 Cl 7 ] 3- anion is also located on a special position of site symmetry and bridges two corner sharing, tetra-hedrally coordinated Cd II atoms. The two Cd atoms and the central Cl atom are colinear. The two sets of terminal chloride ligands on either side of the dumbbell-like anion are rotated relative to each other by 30°. In the crystal, the cations and anions, stacked one above the other along the c -axis direction, are held in place principally by electrostatic inter-actions. There are also C-H⋯Cl and C-H⋯O inter-actions, but these are rather weak. Of the six crystal structures reported to date for ionic salts of [Fe(DMF) 6 ]  n + cations ( n = 2, 3), five contain Fe II ions. The title compound is the second example of a stable compound containing the [Fe(DMF) 6 ] 3+ cation. The existence of both [Fe(DMF) 6 ] 2+ and [Fe(DMF) 6 ] 3+ cations shows that the DMF ligand coordination sphere can accommodate changes in the charge and spin states of the metal centre.

Crystal structure of hexakis(N,N-dimethylformamide-κO)iron(III) μ-chlorido-bis(trichloridocadmium)