LiCr2O4 is Spinel-like structured and crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Cr(2)O6 octahedra and corners with nine equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. In the second Li site, Li(2) is bonded to one O(4) and three equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-64°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Cr(2)O6 octahedra, edges with four equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 51°. In the second Cr site, Cr(2) 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 Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Cr(2), and two equivalent Cr(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing OLiCr3 tetrahedra. In the third O site, O(3) is bonded to one Li(1) and three equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing OLiCr3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(2) and three equivalent Cr(1) atoms to form distorted corner-sharing OLiCr3 tetrahedra.
LiCr2O4 is Spinel-like structured and crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Cr(2)O6 octahedra and corners with nine equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. The Li(1)-O(3) bond length is 1.93 Å. All Li(1)-O(2) bond lengths are 1.95 Å. In the second Li site, Li(2) is bonded to one O(4) and three equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-64°. The Li(2)-O(4) bond length is 1.77 Å. All Li(2)-O(1) bond lengths are 1.96 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Cr(2)O6 octahedra, edges with four equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 51°. The Cr(1)-O(3) bond length is 1.93 Å. The Cr(1)-O(4) bond length is 1.93 Å. Both Cr(1)-O(1) bond lengths are 1.98 Å. Both Cr(1)-O(2) bond lengths are 1.97 Å. In the second Cr site, Cr(2) 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 Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. All Cr(2)-O(1) bond lengths are 1.98 Å. All Cr(2)-O(2) bond lengths are 1.99 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Cr(2), and two equivalent Cr(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing OLiCr3 tetrahedra. In the third O site, O(3) is bonded to one Li(1) and three equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing OLiCr3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(2) and three equivalent Cr(1) atoms to form distorted corner-sharing OLiCr3 tetrahedra.