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ZnF2 is Rutile structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Zn2+ is bonded to six equivalent F1- atoms to form a mixture of edge and corner-sharing ZnF6 octahedra. The corner-sharing octahedral tilt angles are 50°. All Zn–F bond lengths are 2.07 Å. F1- is bonded in a distorted trigonal planar geometry to three equivalent Zn2+ atoms.
ZnF2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pbcn space group. The structure is three-dimensional. Zn2+ is bonded to six equivalent F1- atoms to form a mixture of edge and corner-sharing ZnF6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are a spread of Zn–F bond distances ranging from 2.04–2.12 Å. F1- is bonded in a distorted trigonal planar geometry to three equivalent Zn2+ atoms.