LiCr6O11 crystallizes in the hexagonal P6_3mc space group. Li(1) is bonded in a 3-coordinate geometry to three equivalent O(2) atoms. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with two equivalent Cr(4)O6 octahedra, corners with two equivalent Cr(2)O5 trigonal bipyramids, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Cr site, Cr(2) is bonded to one O(4), one O(5), and three equivalent O(1) atoms to form corner-sharing CrO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-56°. In the third Cr site, Cr(3) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O5 trigonal bipyramids, and  a faceface with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the fourth Cr site, Cr(4) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O5 trigonal bipyramids, and  a faceface with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cr(2), one Cr(3), and one Cr(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cr(4), and two equivalent Cr(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cr(3) and two equivalent Cr(1) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Cr(2) and three equivalent Cr(1) atoms. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Cr(2) and three equivalent Cr(1) atoms.
LiCr6O11 crystallizes in the hexagonal P6_3mc space group. Li(1) is bonded in a 3-coordinate geometry to three equivalent O(2) atoms. All Li(1)-O(2) bond lengths are 2.62 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with two equivalent Cr(4)O6 octahedra, corners with two equivalent Cr(2)O5 trigonal bipyramids, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Cr(1)-O(4) bond length is 2.02 Å. The Cr(1)-O(5) bond length is 2.03 Å. Both Cr(1)-O(2) bond lengths are 1.93 Å. Both Cr(1)-O(3) bond lengths are 1.93 Å. In the second Cr site, Cr(2) is bonded to one O(4), one O(5), and three equivalent O(1) atoms to form corner-sharing CrO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-56°. The Cr(2)-O(4) bond length is 2.10 Å. The Cr(2)-O(5) bond length is 2.10 Å. All Cr(2)-O(1) bond lengths are 1.82 Å. In the third Cr site, Cr(3) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O5 trigonal bipyramids, and  a faceface with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. All Cr(3)-O(1) bond lengths are 2.05 Å. All Cr(3)-O(3) bond lengths are 1.96 Å. In the fourth Cr site, Cr(4) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O5 trigonal bipyramids, and  a faceface with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. All Cr(4)-O(1) bond lengths are 2.05 Å. All Cr(4)-O(2) bond lengths are 1.96 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cr(2), one Cr(3), and one Cr(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cr(4), and two equivalent Cr(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cr(3) and two equivalent Cr(1) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Cr(2) and three equivalent Cr(1) atoms. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Cr(2) and three equivalent Cr(1) atoms.