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FeCl3 is Bismuth triodide structured and crystallizes in the trigonal R-3 space group. The structure is two-dimensional and consists of three FeCl3 sheets oriented in the (0, 0, 1) direction. Fe3+ is bonded to six equivalent Cl1- atoms to form edge-sharing FeCl6 octahedra. All Fe–Cl bond lengths are 2.27 Å. Cl1- is bonded in a water-like geometry to two equivalent Fe3+ atoms.
FeCl2 is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three FeCl2 sheets oriented in the (0, 0, 1) direction. Fe2+ is bonded to six equivalent Cl1- atoms to form edge-sharing FeCl6 octahedra. All Fe–Cl bond lengths are 2.47 Å. Cl1- is bonded in a distorted T-shaped geometry to three equivalent Fe2+ atoms.
FeCl3 crystallizes in the triclinic P1 space group. The structure is one-dimensional and consists of one FeCl3 ribbon oriented in the (1, 0, 0) direction. there are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to five Cl1- atoms to form corner-sharing FeCl5 trigonal bipyramids. There are a spread of Fe–Cl bond distances ranging from 2.13–2.30 Å. In the second Fe3+ site, Fe3+ is bonded in a distorted see-saw-like geometry to four Cl1- atoms. There are a spread of Fe–Cl bond distances ranging from 2.10–2.21 Å. There are six inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Fe3+ atom. In the second Cl1- site, Cl1- is bonded in an L-shaped geometry to two Fe3+ atoms. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Fe3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Fe3+ atom. In the fifth Cl1- site, Cl1- is bonded in an L-shaped geometry to two Fe3+ atoms. In the sixth Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two equivalent Fe3+ atoms.
FeCl is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Fe is bonded in a body-centered cubic geometry to eight equivalent Cl atoms. All Fe–Cl bond lengths are 2.69 Å. Cl is bonded in a body-centered cubic geometry to eight equivalent Fe atoms.