Li9Cr5O12 crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-64°. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. In the fourth Li site, Li(4) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, edges with six equivalent Cr(3)O6 octahedra, and edges with two equivalent Li(2)O4 tetrahedra. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra and edges with six equivalent Cr(1)O6 octahedra. In the third Cr site, Cr(3) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, edges with three equivalent Li(4)O6 octahedra, edges with three equivalent Cr(3)O6 octahedra, and edges with two equivalent Li(2)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), and two equivalent Cr(3) atoms to form distorted OLi3Cr2 trigonal bipyramids that share corners with two equivalent O(3)Li3Cr3 octahedra,  a cornercorner with one O(4)Li3Cr2 trigonal bipyramid, and  an edgeedge with one O(4)Li3Cr2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 68°. In the second O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one Cr(2), and two equivalent Cr(1) atoms. In the third O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), one Li(4), two equivalent Li(3), and two equivalent Cr(3) atoms. In the fourth O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Cr(2), and two equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with two equivalent O(3)Li3Cr3 octahedra,  a cornercorner with one O(4)Li3Cr2 trigonal bipyramid, and edges with five equivalent O(3)Li3Cr3 octahedra. The corner-sharing octahedra are not tilted.
Li9Cr5O12 crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(3) atoms. The Li(1)-O(4) bond length is 1.82 Å. Both Li(1)-O(3) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-64°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(4) bond length is 1.90 Å. Both Li(2)-O(2) bond lengths are 1.87 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. There is one shorter (1.90 Å) and one longer (2.05 Å) Li(3)-O(2) bond length. There is one shorter (2.03 Å) and one longer (2.19 Å) Li(3)-O(3) bond length. In the fourth Li site, Li(4) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, edges with six equivalent Cr(3)O6 octahedra, and edges with two equivalent Li(2)O4 tetrahedra. Both Li(4)-O(4) bond lengths are 2.23 Å. All Li(4)-O(2) bond lengths are 2.19 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. Both Cr(1)-O(1) bond lengths are 2.03 Å. There are two shorter (2.04 Å) and two longer (2.07 Å) Cr(1)-O(3) bond lengths. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra and edges with six equivalent Cr(1)O6 octahedra. Both Cr(2)-O(1) bond lengths are 2.04 Å. All Cr(2)-O(3) bond lengths are 2.05 Å. In the third Cr site, Cr(3) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, edges with three equivalent Li(4)O6 octahedra, edges with three equivalent Cr(3)O6 octahedra, and edges with two equivalent Li(2)O4 tetrahedra. Both Cr(3)-O(4) bond lengths are 2.03 Å. There are two shorter (2.05 Å) and two longer (2.08 Å) Cr(3)-O(2) bond lengths. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), and two equivalent Cr(3) atoms to form distorted OLi3Cr2 trigonal bipyramids that share corners with two equivalent O(3)Li3Cr3 octahedra,  a cornercorner with one O(4)Li3Cr2 trigonal bipyramid, and  an edgeedge with one O(4)Li3Cr2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 68°. In the second O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one Cr(2), and two equivalent Cr(1) atoms. In the third O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), one Li(4), two equivalent Li(3), and two equivalent Cr(3) atoms. In the fourth O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Cr(2), and two equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with two equivalent O(3)Li3Cr3 octahedra,  a cornercorner with one O(4)Li3Cr2 trigonal bipyramid, and edges with five equivalent O(3)Li3Cr3 octahedra. The corner-sharing octahedra are not tilted.