Li2CrSiO4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. Cr(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), and three equivalent O(4) atoms. 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. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one Si(1) atom to form distorted OLi3Si tetrahedra that share corners with four equivalent O(2)Li2CrSi tetrahedra, corners with four equivalent O(3)Li2CrSi tetrahedra, and  an edgeedge with one O(1)Li3Si tetrahedra. 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 OLi2CrSi tetrahedra that share corners with four equivalent O(3)Li2CrSi tetrahedra and corners with four equivalent O(1)Li3Si tetrahedra. 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 OLi2CrSi tetrahedra that share corners with four equivalent O(2)Li2CrSi tetrahedra and corners with four equivalent O(1)Li3Si tetrahedra. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to three equivalent Cr(1) and one Si(1) atom.
Li2CrSiO4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 1.98 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. The Li(2)-O(1) bond length is 1.92 Å. The Li(2)-O(2) bond length is 1.97 Å. The Li(2)-O(3) bond length is 1.99 Å. Cr(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), and three equivalent O(4) atoms. The Cr(1)-O(2) bond length is 2.01 Å. The Cr(1)-O(3) bond length is 2.05 Å. There are a spread of Cr(1)-O(4) bond distances ranging from 2.17-2.66 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. The Si(1)-O(1) bond length is 1.62 Å. The Si(1)-O(2) bond length is 1.66 Å. The Si(1)-O(3) bond length is 1.67 Å. The Si(1)-O(4) bond length is 1.69 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one Si(1) atom to form distorted OLi3Si tetrahedra that share corners with four equivalent O(2)Li2CrSi tetrahedra, corners with four equivalent O(3)Li2CrSi tetrahedra, and  an edgeedge with one O(1)Li3Si tetrahedra. 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 OLi2CrSi tetrahedra that share corners with four equivalent O(3)Li2CrSi tetrahedra and corners with four equivalent O(1)Li3Si tetrahedra. 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 OLi2CrSi tetrahedra that share corners with four equivalent O(2)Li2CrSi tetrahedra and corners with four equivalent O(1)Li3Si tetrahedra. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to three equivalent Cr(1) and one Si(1) atom.