Li4Cr2Si3O10 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(5), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra, corners with three equivalent Cr(1)O5 trigonal bipyramids,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded in a distorted pentagonal planar geometry to one O(3), two equivalent O(1), and two equivalent O(4) atoms. Cr(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(5) atoms to form CrO5 trigonal bipyramids that share  a cornercorner with one Si(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one Si(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent Cr(1)O5 trigonal bipyramids. In the second Si site, Si(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form SiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra and corners with two equivalent Cr(1)O5 trigonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Cr(1), and one Si(2) atom to form a mixture of distorted corner and edge-sharing OLi2CrSi trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cr(1), and one Si(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLi2CrSi tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Cr(1), and one Si(1) atom.
Li4Cr2Si3O10 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(5), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra, corners with three equivalent Cr(1)O5 trigonal bipyramids,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. The Li(1)-O(3) bond length is 1.97 Å. The Li(1)-O(5) bond length is 2.20 Å. There is one shorter (1.90 Å) and one longer (1.96 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a distorted pentagonal planar geometry to one O(3), two equivalent O(1), and two equivalent O(4) atoms. The Li(2)-O(3) bond length is 1.99 Å. There is one shorter (2.08 Å) and one longer (2.09 Å) Li(2)-O(1) bond length. There is one shorter (2.42 Å) and one longer (2.44 Å) Li(2)-O(4) bond length. Cr(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(5) atoms to form CrO5 trigonal bipyramids that share  a cornercorner with one Si(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. The Cr(1)-O(1) bond length is 2.10 Å. The Cr(1)-O(2) bond length is 2.41 Å. The Cr(1)-O(3) bond length is 2.11 Å. There is one shorter (2.09 Å) and one longer (2.14 Å) Cr(1)-O(5) bond length. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one Si(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent Cr(1)O5 trigonal bipyramids. The Si(1)-O(2) bond length is 1.61 Å. The Si(1)-O(3) bond length is 1.65 Å. The Si(1)-O(4) bond length is 1.69 Å. The Si(1)-O(5) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form SiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra and corners with two equivalent Cr(1)O5 trigonal bipyramids. Both Si(2)-O(1) bond lengths are 1.62 Å. Both Si(2)-O(4) bond lengths are 1.66 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Cr(1), and one Si(2) atom to form a mixture of distorted corner and edge-sharing OLi2CrSi trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cr(1), and one Si(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLi2CrSi tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Cr(1), and one Si(1) atom.