Li2CrSiO4 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 tetrahedra that share corners with four equivalent Cr(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 trigonal pyramid. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Cr(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. Cr(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CrO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 trigonal pyramid. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Cr(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 trigonal pyramid. 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(1), one Li(2), one Cr(1), and one Si(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), and one Si(1) atom to form a mixture of edge and corner-sharing OLi2CrSi trigonal pyramids. 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 edge and corner-sharing OLi2CrSi trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Cr(1), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLi2CrSi tetrahedra.
Li2CrSiO4 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 tetrahedra that share corners with four equivalent Cr(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(2) bond length is 1.94 Å. The Li(1)-O(3) bond length is 1.91 Å. The Li(1)-O(4) bond length is 2.04 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cr(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Cr(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The Li(2)-O(1) bond length is 2.20 Å. The Li(2)-O(2) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.19 Å. The Li(2)-O(4) bond length is 2.07 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CrO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Cr(1)-O(1) bond length is 2.12 Å. The Cr(1)-O(2) bond length is 2.01 Å. The Cr(1)-O(3) bond length is 2.04 Å. The Cr(1)-O(4) bond length is 2.13 Å. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Cr(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.66 Å. The Si(1)-O(3) bond length is 1.66 Å. The Si(1)-O(4) bond length is 1.65 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(1), one Li(2), one Cr(1), and one Si(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), and one Si(1) atom to form a mixture of edge and corner-sharing OLi2CrSi trigonal pyramids. 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 edge and corner-sharing OLi2CrSi trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Cr(1), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLi2CrSi tetrahedra.