Li9Cr3(WO4)7 crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(7), two equivalent O(6), and two equivalent O(8) atoms. There are three inequivalent W sites. In the first W site, W(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form distorted WO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra and edges with three equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. In the second W site, W(1) is bonded to one O(1), one O(7), two equivalent O(5), and two equivalent O(6) atoms to form distorted WO6 octahedra that share  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. In the third W site, W(3) is bonded to one O(4), one O(8), and two equivalent O(3) atoms to form WO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. Cr(1) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O4 tetrahedra, and edges with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. There are eight inequivalent O sites. In the first O site, O(5) is bonded to two equivalent Li(1), one W(2), two equivalent W(1), and one Cr(1) atom to form edge-sharing OLi2CrW3 octahedra. In the second O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one W(1), and one Cr(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one W(3), and one Cr(1) atom. In the fourth O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Li(2) and three equivalent W(1) atoms. In the fifth O site, O(8) is bonded in a trigonal planar geometry to two equivalent Li(2) and one W(3) atom. In the sixth O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(1), and one W(1) atom. In the seventh O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one W(2), and one Cr(1) atom. In the eighth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one W(3) atom.
Li9Cr3(WO4)7 crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.27 Å. The Li(1)-O(2) bond length is 2.35 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.02 Å. The Li(1)-O(5) bond length is 2.49 Å. The Li(1)-O(6) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(7), two equivalent O(6), and two equivalent O(8) atoms. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(7) bond length is 2.66 Å. Both Li(2)-O(6) bond lengths are 2.27 Å. Both Li(2)-O(8) bond lengths are 2.02 Å. There are three inequivalent W sites. In the first W site, W(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form distorted WO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra and edges with three equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. All W(2)-O(2) bond lengths are 1.84 Å. All W(2)-O(5) bond lengths are 2.20 Å. In the second W site, W(1) is bonded to one O(1), one O(7), two equivalent O(5), and two equivalent O(6) atoms to form distorted WO6 octahedra that share  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The W(1)-O(1) bond length is 1.82 Å. The W(1)-O(7) bond length is 2.16 Å. Both W(1)-O(5) bond lengths are 2.20 Å. Both W(1)-O(6) bond lengths are 1.95 Å. In the third W site, W(3) is bonded to one O(4), one O(8), and two equivalent O(3) atoms to form WO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The W(3)-O(4) bond length is 1.79 Å. The W(3)-O(8) bond length is 1.80 Å. Both W(3)-O(3) bond lengths are 1.84 Å. Cr(1) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O4 tetrahedra, and edges with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. The Cr(1)-O(2) bond length is 2.12 Å. The Cr(1)-O(5) bond length is 2.38 Å. Both Cr(1)-O(3) bond lengths are 2.05 Å. Both Cr(1)-O(6) bond lengths are 1.99 Å. There are eight inequivalent O sites. In the first O site, O(5) is bonded to two equivalent Li(1), one W(2), two equivalent W(1), and one Cr(1) atom to form edge-sharing OLi2CrW3 octahedra. In the second O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one W(1), and one Cr(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one W(3), and one Cr(1) atom. In the fourth O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Li(2) and three equivalent W(1) atoms. In the fifth O site, O(8) is bonded in a trigonal planar geometry to two equivalent Li(2) and one W(3) atom. In the sixth O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(1), and one W(1) atom. In the seventh O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one W(2), and one Cr(1) atom. In the eighth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one W(3) atom.