Li5MnP2(O4F)2 crystallizes in the trigonal P3 space group. There are nine inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), one O(5), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one Li(5)O3F3 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(4)O3F3 octahedra, and edges with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 38°. In the second Li site, Li(2) is bonded to three equivalent O(3) and three equivalent F(2) atoms to form distorted LiO3F3 octahedra that share corners with three equivalent Mn(1)O4F2 octahedra, corners with three equivalent P(1)O4 tetrahedra, edges with three equivalent Li(1)O4F2 octahedra, and  a faceface with one Li(3)O3F3 octahedra. The corner-sharing octahedral tilt angles are 35°. In the third Li site, Li(3) is bonded to three equivalent O(2) and three equivalent F(2) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent P(1)O4 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra, and  a faceface with one Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles are 38°. In the fourth Li site, Li(4) is bonded to three equivalent O(5) and three equivalent F(1) atoms to form distorted LiO3F3 octahedra that share corners with three equivalent Mn(1)O4F2 octahedra, corners with three equivalent P(2)O4 tetrahedra, edges with three equivalent Li(1)O4F2 octahedra, and  a faceface with one Li(5)O3F3 octahedra. The corner-sharing octahedral tilt angles are 35°. In the fifth Li site, Li(5) is bonded to three equivalent O(6) and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent P(2)O4 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra, and  a faceface with one Li(4)O3F3 octahedra. The corner-sharing octahedral tilt angles are 38°. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(8), and one F(2) atom. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and one F(1) atom. In the eighth Li site, Li(8) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and faces with two equivalent Li(9)O6 octahedra. In the ninth Li site, Li(9) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and faces with two equivalent Li(8)O6 octahedra. Mn(1) is bonded to one O(1), one O(2), one O(4), one O(6), one F(1), and one F(2) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one Li(4)O3F3 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra, and edges with two equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 35°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one Li(8)O6 octahedra,  a cornercorner with one Li(9)O6 octahedra, corners with two equivalent Li(1)O4F2 octahedra, and corners with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-63°. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O3F3 octahedra,  a cornercorner with one Li(5)O3F3 octahedra,  a cornercorner with one Li(8)O6 octahedra,  a cornercorner with one Li(9)O6 octahedra, corners with two equivalent Li(1)O4F2 octahedra, and corners with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(6), one Mn(1), and one P(2) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(6), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(6), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(7), one Mn(1), and one P(1) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Li(7), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one Li(7), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(7), one Li(8), one Li(9), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one Li(8), one Li(9), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one Li(7), and one Mn(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(6), and one Mn(1) atom.
Li5MnP2(O4F)2 crystallizes in the trigonal P3 space group. There are nine inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), one O(5), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one Li(5)O3F3 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(4)O3F3 octahedra, and edges with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 38°. The Li(1)-O(1) bond length is 2.21 Å. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-O(4) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.00 Å. The Li(1)-F(1) bond length is 2.26 Å. The Li(1)-F(2) bond length is 2.31 Å. In the second Li site, Li(2) is bonded to three equivalent O(3) and three equivalent F(2) atoms to form distorted LiO3F3 octahedra that share corners with three equivalent Mn(1)O4F2 octahedra, corners with three equivalent P(1)O4 tetrahedra, edges with three equivalent Li(1)O4F2 octahedra, and  a faceface with one Li(3)O3F3 octahedra. The corner-sharing octahedral tilt angles are 35°. All Li(2)-O(3) bond lengths are 2.11 Å. All Li(2)-F(2) bond lengths are 2.16 Å. In the third Li site, Li(3) is bonded to three equivalent O(2) and three equivalent F(2) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent P(1)O4 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra, and  a faceface with one Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles are 38°. All Li(3)-O(2) bond lengths are 2.14 Å. All Li(3)-F(2) bond lengths are 2.03 Å. In the fourth Li site, Li(4) is bonded to three equivalent O(5) and three equivalent F(1) atoms to form distorted LiO3F3 octahedra that share corners with three equivalent Mn(1)O4F2 octahedra, corners with three equivalent P(2)O4 tetrahedra, edges with three equivalent Li(1)O4F2 octahedra, and  a faceface with one Li(5)O3F3 octahedra. The corner-sharing octahedral tilt angles are 35°. All Li(4)-O(5) bond lengths are 2.14 Å. All Li(4)-F(1) bond lengths are 2.16 Å. In the fifth Li site, Li(5) is bonded to three equivalent O(6) and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent P(2)O4 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra, and  a faceface with one Li(4)O3F3 octahedra. The corner-sharing octahedral tilt angles are 38°. All Li(5)-O(6) bond lengths are 2.14 Å. All Li(5)-F(1) bond lengths are 2.04 Å. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(8), and one F(2) atom. The Li(6)-O(1) bond length is 2.06 Å. The Li(6)-O(2) bond length is 2.40 Å. The Li(6)-O(3) bond length is 2.05 Å. The Li(6)-O(8) bond length is 2.49 Å. The Li(6)-F(2) bond length is 1.92 Å. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and one F(1) atom. The Li(7)-O(4) bond length is 2.07 Å. The Li(7)-O(5) bond length is 2.06 Å. The Li(7)-O(6) bond length is 2.41 Å. The Li(7)-O(7) bond length is 2.43 Å. The Li(7)-F(1) bond length is 1.94 Å. In the eighth Li site, Li(8) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and faces with two equivalent Li(9)O6 octahedra. All Li(8)-O(7) bond lengths are 2.47 Å. All Li(8)-O(8) bond lengths are 2.26 Å. In the ninth Li site, Li(9) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and faces with two equivalent Li(8)O6 octahedra. All Li(9)-O(7) bond lengths are 2.30 Å. All Li(9)-O(8) bond lengths are 2.44 Å. Mn(1) is bonded to one O(1), one O(2), one O(4), one O(6), one F(1), and one F(2) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one Li(4)O3F3 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra, and edges with two equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 35°. The Mn(1)-O(1) bond length is 2.01 Å. The Mn(1)-O(2) bond length is 1.91 Å. The Mn(1)-O(4) bond length is 2.02 Å. The Mn(1)-O(6) bond length is 1.91 Å. The Mn(1)-F(1) bond length is 2.15 Å. The Mn(1)-F(2) bond length is 2.14 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one Li(8)O6 octahedra,  a cornercorner with one Li(9)O6 octahedra, corners with two equivalent Li(1)O4F2 octahedra, and corners with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-63°. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O3F3 octahedra,  a cornercorner with one Li(5)O3F3 octahedra,  a cornercorner with one Li(8)O6 octahedra,  a cornercorner with one Li(9)O6 octahedra, corners with two equivalent Li(1)O4F2 octahedra, and corners with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.58 Å. The P(2)-O(8) bond length is 1.53 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(6), one Mn(1), and one P(2) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(6), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(6), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(7), one Mn(1), and one P(1) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Li(7), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one Li(7), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(7), one Li(8), one Li(9), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one Li(8), one Li(9), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one Li(7), and one Mn(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(6), and one Mn(1) atom.