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HgF2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Hg2+ is bonded in a body-centered cubic geometry to eight equivalent F1- atoms. All Hg–F bond lengths are 2.45 Å. F1- is bonded to four equivalent Hg2+ atoms to form a mixture of edge and corner-sharing FHg4 tetrahedra.
HgF2 is Hydrophilite structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Hg2+ is bonded to six equivalent F1- atoms to form a mixture of corner and edge-sharing HgF6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are two shorter (2.27 Å) and four longer (2.39 Å) Hg–F bond lengths. F1- is bonded in a trigonal planar geometry to three equivalent Hg2+ atoms.