Li6CrO6 crystallizes in the monoclinic Cc space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(4), and one O(5) atom. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra,  a cornercorner with one Li(6)O4 trigonal pyramid,  an edgeedge with one Li(3)O4 tetrahedra,  an edgeedge with one Cr(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 trigonal pyramid. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with three equivalent Li(6)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(5)O4 tetrahedra, corners with three equivalent Cr(1)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(6)O4 trigonal pyramid. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Cr(1)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(6)O4 trigonal pyramid. In the sixth Li site, Li(6) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. Cr(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form CrO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(6)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), and one Li(6) atom to form a mixture of edge and corner-sharing OLi5 trigonal bipyramids. In the second O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(6), and one Cr(1) atom. In the third O site, O(6) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one Li(6), and one Cr(1) atom. In the fourth O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(5), and one Cr(1) atom. In the fifth O site, O(2) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Li(5), and one Cr(1) atom. In the sixth O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Li(6) atom to form a mixture of edge and corner-sharing OLi5 trigonal bipyramids.
Li6CrO6 crystallizes in the monoclinic Cc space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(4), and one O(5) atom. The Li(1)-O(1) bond length is 2.50 Å. The Li(1)-O(3) bond length is 1.87 Å. The Li(1)-O(4) bond length is 1.82 Å. The Li(1)-O(5) bond length is 2.21 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra,  a cornercorner with one Li(6)O4 trigonal pyramid,  an edgeedge with one Li(3)O4 tetrahedra,  an edgeedge with one Cr(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 trigonal pyramid. The Li(2)-O(1) bond length is 2.14 Å. The Li(2)-O(3) bond length is 1.86 Å. The Li(2)-O(4) bond length is 1.86 Å. The Li(2)-O(5) bond length is 2.11 Å. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with three equivalent Li(6)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. The Li(3)-O(2) bond length is 2.09 Å. The Li(3)-O(3) bond length is 1.93 Å. The Li(3)-O(4) bond length is 1.93 Å. The Li(3)-O(5) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(5)O4 tetrahedra, corners with three equivalent Cr(1)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(6)O4 trigonal pyramid. The Li(4)-O(1) bond length is 2.07 Å. The Li(4)-O(2) bond length is 2.07 Å. The Li(4)-O(3) bond length is 1.88 Å. The Li(4)-O(6) bond length is 2.13 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Cr(1)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(6)O4 trigonal pyramid. The Li(5)-O(1) bond length is 2.17 Å. The Li(5)-O(2) bond length is 2.09 Å. The Li(5)-O(4) bond length is 1.88 Å. The Li(5)-O(6) bond length is 2.04 Å. In the sixth Li site, Li(6) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. The Li(6)-O(3) bond length is 1.82 Å. The Li(6)-O(4) bond length is 1.87 Å. The Li(6)-O(5) bond length is 2.27 Å. The Li(6)-O(6) bond length is 2.42 Å. Cr(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form CrO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(6)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 tetrahedra. The Cr(1)-O(1) bond length is 1.69 Å. The Cr(1)-O(2) bond length is 1.68 Å. The Cr(1)-O(5) bond length is 1.67 Å. The Cr(1)-O(6) bond length is 1.67 Å. There are six inequivalent O sites. In the first O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), and one Li(6) atom to form a mixture of edge and corner-sharing OLi5 trigonal bipyramids. In the second O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(6), and one Cr(1) atom. In the third O site, O(6) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one Li(6), and one Cr(1) atom. In the fourth O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(5), and one Cr(1) atom. In the fifth O site, O(2) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Li(5), and one Cr(1) atom. In the sixth O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Li(6) atom to form a mixture of edge and corner-sharing OLi5 trigonal bipyramids.