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MgCl2 is trigonal omega structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one MgCl2 sheet oriented in the (0, 0, 1) direction. Mg2+ is bonded to six equivalent Cl1- atoms to form edge-sharing MgCl6 octahedra. All Mg–Cl bond lengths are 2.53 Å. Cl1- is bonded in a distorted T-shaped geometry to three equivalent Mg2+ atoms.
MgCl2 crystallizes in the triclinic P-1 space group. The structure is two-dimensional and consists of one MgCl2 sheet oriented in the (1, 0, 0) direction. Mg2+ is bonded to four Cl1- atoms to form a mixture of edge and corner-sharing MgCl4 tetrahedra. There are a spread of Mg–Cl bond distances ranging from 2.35–2.38 Å. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in an L-shaped geometry to two equivalent Mg2+ atoms. In the second Cl1- site, Cl1- is bonded in a linear geometry to two equivalent Mg2+ atoms. In the third Cl1- site, Cl1- is bonded in a linear geometry to two equivalent Mg2+ atoms.
MgCl2 crystallizes in the tetragonal P-4m2 space group. The structure is two-dimensional and consists of one MgCl2 sheet oriented in the (0, 0, 1) direction. Mg2+ is bonded to four equivalent Cl1- atoms to form corner-sharing MgCl4 tetrahedra. All Mg–Cl bond lengths are 2.37 Å. Cl1- is bonded in a water-like geometry to two equivalent Mg2+ atoms.