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CdF2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Cd2+ is bonded in a body-centered cubic geometry to eight equivalent F1- atoms. All Cd–F bond lengths are 2.38 Å. F1- is bonded to four equivalent Cd2+ atoms to form a mixture of corner and edge-sharing FCd4 tetrahedra.
CdF2 is Cotunnite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Cd2+ is bonded in a 9-coordinate geometry to nine F1- atoms. There are a spread of Cd–F bond distances ranging from 2.31–2.82 Å. There are two inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to five equivalent Cd2+ atoms. In the second F1- site, F1- is bonded to four equivalent Cd2+ atoms to form a mixture of edge and corner-sharing FCd4 tetrahedra.