Li4WCr5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), and two equivalent O(2) atoms. W(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form WO6 octahedra that share edges with six equivalent Cr(2)O6 octahedra. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CrO6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form CrO6 octahedra that share edges with three equivalent W(1)O6 octahedra and edges with three equivalent Cr(2)O6 octahedra. In the third Cr site, Cr(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CrO6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one W(1), and two equivalent Cr(2) atoms to form distorted OLiCr2W trigonal pyramids that share  a cornercorner with one O(3)Li2Cr3 square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with five equivalent O(1)LiCr2W trigonal pyramids, and edges with two equivalent O(1)LiCr2W trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Cr(3), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with three equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(1)LiCr2W trigonal pyramids, edges with three equivalent O(3)Li2Cr3 square pyramids, and edges with four equivalent O(2)Li2Cr3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Cr(3), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share  a cornercorner with one O(3)Li2Cr3 square pyramid, corners with four equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(1)LiCr2W trigonal pyramids,  an edgeedge with one O(3)Li2Cr3 square pyramid, and edges with six equivalent O(2)Li2Cr3 square pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one W(1) and two equivalent Cr(2) atoms.
Li4WCr5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(3) bond length is 2.05 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Li(1)-O(2) bond length. W(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form WO6 octahedra that share edges with six equivalent Cr(2)O6 octahedra. Both W(1)-O(4) bond lengths are 1.95 Å. All W(1)-O(1) bond lengths are 2.05 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CrO6 octahedra. Both Cr(1)-O(3) bond lengths are 2.06 Å. There are two shorter (2.02 Å) and two longer (2.07 Å) Cr(1)-O(2) bond lengths. In the second Cr site, Cr(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form CrO6 octahedra that share edges with three equivalent W(1)O6 octahedra and edges with three equivalent Cr(2)O6 octahedra. Both Cr(2)-O(4) bond lengths are 2.03 Å. There are two shorter (2.01 Å) and two longer (2.03 Å) Cr(2)-O(1) bond lengths. In the third Cr site, Cr(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CrO6 octahedra. Both Cr(3)-O(3) bond lengths are 2.00 Å. All Cr(3)-O(2) bond lengths are 2.08 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one W(1), and two equivalent Cr(2) atoms to form distorted OLiCr2W trigonal pyramids that share  a cornercorner with one O(3)Li2Cr3 square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with five equivalent O(1)LiCr2W trigonal pyramids, and edges with two equivalent O(1)LiCr2W trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Cr(3), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with three equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(1)LiCr2W trigonal pyramids, edges with three equivalent O(3)Li2Cr3 square pyramids, and edges with four equivalent O(2)Li2Cr3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Cr(3), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share  a cornercorner with one O(3)Li2Cr3 square pyramid, corners with four equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(1)LiCr2W trigonal pyramids,  an edgeedge with one O(3)Li2Cr3 square pyramid, and edges with six equivalent O(2)Li2Cr3 square pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one W(1) and two equivalent Cr(2) atoms.