Li3Mn2C3O9F crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(7), one O(8), and one O(9) atom. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form a mixture of edge and corner-sharing LiO5F octahedra. The corner-sharing octahedral tilt angles are 75°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(9), and one F(1) atom to form a mixture of edge and corner-sharing LiO5F octahedra. The corner-sharing octahedral tilt angles are 75°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(7), one O(8), and two equivalent O(9) atoms. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(7), one O(8), two equivalent O(6), and two equivalent F(1) atoms. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(6) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(3), one O(5), and one O(7) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(4), one O(8), and one O(9) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Mn(1), and one C(1) atom to form distorted OLi2MnC tetrahedra that share  a cornercorner with one O(7)LiMn2C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, corners with three equivalent O(2)Li3C tetrahedra, and  an edgeedge with one O(3)Li2MnC trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one C(1) atom to form distorted OLi3C tetrahedra that share  a cornercorner with one O(7)LiMn2C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, corners with three equivalent O(1)Li2MnC tetrahedra, and  an edgeedge with one O(3)Li2MnC trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(1), and one C(2) atom to form distorted OLi2MnC trigonal pyramids that share  a cornercorner with one F(1)Li2Mn2 tetrahedra, corners with three equivalent O(7)LiMn2C tetrahedra,  an edgeedge with one O(1)Li2MnC tetrahedra, and  an edgeedge with one O(2)Li3C tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Mn(1), and one C(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), and one C(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Mn(2) and one C(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one Mn(1), one Mn(2), and one C(2) atom to form distorted OLiMn2C tetrahedra that share  a cornercorner with one O(1)Li2MnC tetrahedra,  a cornercorner with one O(2)Li3C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, and corners with three equivalent O(3)Li2MnC trigonal pyramids. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one C(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Li(1), one Li(3), two equivalent Mn(1), and one C(3) atom. F(1) is bonded to one Li(2), one Li(3), and two equivalent Mn(2) atoms to form FLi2Mn2 tetrahedra that share corners with two equivalent O(1)Li2MnC tetrahedra, corners with two equivalent O(2)Li3C tetrahedra, corners with two equivalent O(7)LiMn2C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, and  a cornercorner with one O(3)Li2MnC trigonal pyramid.
Li3Mn2C3O9F crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(7), one O(8), and one O(9) atom. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.24 Å. The Li(1)-O(7) bond length is 2.07 Å. The Li(1)-O(8) bond length is 2.41 Å. The Li(1)-O(9) bond length is 2.31 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form a mixture of edge and corner-sharing LiO5F octahedra. The corner-sharing octahedral tilt angles are 75°. The Li(2)-O(1) bond length is 2.21 Å. The Li(2)-O(2) bond length is 2.20 Å. The Li(2)-O(3) bond length is 2.20 Å. The Li(2)-O(4) bond length is 2.26 Å. The Li(2)-O(5) bond length is 2.13 Å. The Li(2)-F(1) bond length is 2.26 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(9), and one F(1) atom to form a mixture of edge and corner-sharing LiO5F octahedra. The corner-sharing octahedral tilt angles are 75°. The Li(3)-O(1) bond length is 2.21 Å. The Li(3)-O(2) bond length is 2.14 Å. The Li(3)-O(4) bond length is 2.14 Å. The Li(3)-O(5) bond length is 2.10 Å. The Li(3)-O(9) bond length is 2.29 Å. The Li(3)-F(1) bond length is 2.16 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(7), one O(8), and two equivalent O(9) atoms. The Mn(1)-O(1) bond length is 2.20 Å. The Mn(1)-O(3) bond length is 2.20 Å. The Mn(1)-O(4) bond length is 2.24 Å. The Mn(1)-O(7) bond length is 2.20 Å. The Mn(1)-O(8) bond length is 2.20 Å. There is one shorter (2.50 Å) and one longer (2.57 Å) Mn(1)-O(9) bond length. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(7), one O(8), two equivalent O(6), and two equivalent F(1) atoms. The Mn(2)-O(7) bond length is 2.30 Å. The Mn(2)-O(8) bond length is 2.30 Å. There is one shorter (2.16 Å) and one longer (2.23 Å) Mn(2)-O(6) bond length. There is one shorter (2.13 Å) and one longer (2.16 Å) Mn(2)-F(1) bond length. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(6) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.28 Å. The C(1)-O(6) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(3), one O(5), and one O(7) atom. The C(2)-O(3) bond length is 1.30 Å. The C(2)-O(5) bond length is 1.28 Å. The C(2)-O(7) bond length is 1.33 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(4), one O(8), and one O(9) atom. The C(3)-O(4) bond length is 1.29 Å. The C(3)-O(8) bond length is 1.31 Å. The C(3)-O(9) bond length is 1.30 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Mn(1), and one C(1) atom to form distorted OLi2MnC tetrahedra that share  a cornercorner with one O(7)LiMn2C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, corners with three equivalent O(2)Li3C tetrahedra, and  an edgeedge with one O(3)Li2MnC trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one C(1) atom to form distorted OLi3C tetrahedra that share  a cornercorner with one O(7)LiMn2C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, corners with three equivalent O(1)Li2MnC tetrahedra, and  an edgeedge with one O(3)Li2MnC trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(1), and one C(2) atom to form distorted OLi2MnC trigonal pyramids that share  a cornercorner with one F(1)Li2Mn2 tetrahedra, corners with three equivalent O(7)LiMn2C tetrahedra,  an edgeedge with one O(1)Li2MnC tetrahedra, and  an edgeedge with one O(2)Li3C tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Mn(1), and one C(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), and one C(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Mn(2) and one C(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one Mn(1), one Mn(2), and one C(2) atom to form distorted OLiMn2C tetrahedra that share  a cornercorner with one O(1)Li2MnC tetrahedra,  a cornercorner with one O(2)Li3C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, and corners with three equivalent O(3)Li2MnC trigonal pyramids. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one C(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Li(1), one Li(3), two equivalent Mn(1), and one C(3) atom. F(1) is bonded to one Li(2), one Li(3), and two equivalent Mn(2) atoms to form FLi2Mn2 tetrahedra that share corners with two equivalent O(1)Li2MnC tetrahedra, corners with two equivalent O(2)Li3C tetrahedra, corners with two equivalent O(7)LiMn2C tetrahedra, corners with two equivalent F(1)Li2Mn2 tetrahedra, and  a cornercorner with one O(3)Li2MnC trigonal pyramid.