LiCoSiO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-74°. Co(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Si(1)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. Si(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Co(1), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLiCo2Si tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one Si(1) atom.
LiCoSiO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-74°. Both Li(1)-O(1) bond lengths are 2.10 Å. Both Li(1)-O(2) bond lengths are 1.96 Å. Co(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Si(1)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. Both Co(1)-O(2) bond lengths are 1.88 Å. All Co(1)-O(1) bond lengths are 2.13 Å. Si(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. Both Si(1)-O(1) bond lengths are 1.66 Å. Both Si(1)-O(2) bond lengths are 1.64 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Co(1), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLiCo2Si tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one Si(1) atom.