Mn2(PO4)F crystallizes in the monoclinic C2/c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent F(1) atoms to form distorted MnO4F2 pentagonal pyramids that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 40-70°. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent F(1) atoms to form distorted MnO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O4F2 pentagonal pyramids. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent Mn(2)O4F2 octahedra and corners with four equivalent Mn(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 46-57°. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Mn(1) and one P(1) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Mn(2) and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. F(1) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form distorted edge-sharing FMn4 tetrahedra.
Mn2(PO4)F crystallizes in the monoclinic C2/c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent F(1) atoms to form distorted MnO4F2 pentagonal pyramids that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 40-70°. The Mn(1)-O(2) bond length is 2.19 Å. The Mn(1)-O(4) bond length is 2.18 Å. There is one shorter (2.15 Å) and one longer (2.24 Å) Mn(1)-O(3) bond length. There is one shorter (2.15 Å) and one longer (2.57 Å) Mn(1)-F(1) bond length. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent F(1) atoms to form distorted MnO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O4F2 pentagonal pyramids. The Mn(2)-O(2) bond length is 2.16 Å. The Mn(2)-O(4) bond length is 2.16 Å. There is one shorter (2.16 Å) and one longer (2.23 Å) Mn(2)-O(1) bond length. There is one shorter (2.17 Å) and one longer (2.40 Å) Mn(2)-F(1) bond length. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent Mn(2)O4F2 octahedra and corners with four equivalent Mn(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 46-57°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Mn(1) and one P(1) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Mn(2) and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. F(1) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form distorted edge-sharing FMn4 tetrahedra.