MnF2 is Rutile structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Mn2+ is bonded to six equivalent F1- atoms to form a mixture of corner and edge-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are two shorter (2.14 Å) and four longer (2.17 Å) Mn–F bond lengths. F1- is bonded in a trigonal planar geometry to three equivalent Mn2+ atoms.