Li5Cr2O8 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Cr(2)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with two equivalent Cr(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and edges with two equivalent Li(3)O5 trigonal bipyramids. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra,  a cornercorner with one Cr(1)O4 tetrahedra, corners with two equivalent Cr(2)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Cr(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Cr(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Cr(1)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with two equivalent Cr(2)O4 tetrahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form CrO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CrO4 tetrahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(3)O5 trigonal bipyramids. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(4), one Li(5), and one Cr(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(5), and one Cr(2) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Cr(2) atom. In the fourth O site, O(4) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one Cr(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Cr(1) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Cr(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Li(5), and one Cr(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one Li(5), and one Cr(1) atom.
Li5Cr2O8 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Cr(2)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(8) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with two equivalent Cr(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and edges with two equivalent Li(3)O5 trigonal bipyramids. The Li(2)-O(3) bond length is 2.04 Å. The Li(2)-O(4) bond length is 2.01 Å. The Li(2)-O(5) bond length is 1.93 Å. The Li(2)-O(6) bond length is 1.90 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra,  a cornercorner with one Cr(1)O4 tetrahedra, corners with two equivalent Cr(2)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Cr(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. The Li(3)-O(3) bond length is 2.24 Å. The Li(3)-O(4) bond length is 2.15 Å. The Li(3)-O(5) bond length is 2.02 Å. The Li(3)-O(6) bond length is 2.13 Å. The Li(3)-O(7) bond length is 2.21 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Cr(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Cr(1)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Li(4)-O(1) bond length is 2.09 Å. The Li(4)-O(5) bond length is 2.08 Å. The Li(4)-O(6) bond length is 1.97 Å. The Li(4)-O(7) bond length is 1.90 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with two equivalent Cr(2)O4 tetrahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. The Li(5)-O(1) bond length is 2.06 Å. The Li(5)-O(2) bond length is 2.06 Å. The Li(5)-O(7) bond length is 2.03 Å. The Li(5)-O(8) bond length is 1.90 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form CrO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Cr(1)-O(5) bond length is 1.73 Å. The Cr(1)-O(6) bond length is 1.73 Å. The Cr(1)-O(7) bond length is 1.72 Å. The Cr(1)-O(8) bond length is 1.73 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CrO4 tetrahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(3)O5 trigonal bipyramids. The Cr(2)-O(1) bond length is 1.66 Å. The Cr(2)-O(2) bond length is 1.66 Å. The Cr(2)-O(3) bond length is 1.68 Å. The Cr(2)-O(4) bond length is 1.69 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(4), one Li(5), and one Cr(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(5), and one Cr(2) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Cr(2) atom. In the fourth O site, O(4) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one Cr(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Cr(1) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Cr(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Li(5), and one Cr(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one Li(5), and one Cr(1) atom.