LiCoSiO4 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and edges with two equivalent Co(1)O5 trigonal bipyramids. Co(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form CoO5 trigonal bipyramids that share corners with three equivalent Si(1)O4 tetrahedra, corners with two equivalent Co(1)O5 trigonal bipyramids,  an edgeedge with one Si(1)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. 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 three equivalent Co(1)O5 trigonal bipyramids, corners with four equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one Co(1)O5 trigonal bipyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Co(1), and one Si(1) atom to form corner-sharing OLi2CoSi trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Co(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one Si(1) atom.
LiCoSiO4 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and edges with two equivalent Co(1)O5 trigonal bipyramids. The Li(1)-O(3) bond length is 1.97 Å. The Li(1)-O(4) bond length is 1.99 Å. There is one shorter (2.01 Å) and one longer (2.02 Å) Li(1)-O(1) bond length. Co(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form CoO5 trigonal bipyramids that share corners with three equivalent Si(1)O4 tetrahedra, corners with two equivalent Co(1)O5 trigonal bipyramids,  an edgeedge with one Si(1)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The Co(1)-O(1) bond length is 1.95 Å. The Co(1)-O(3) bond length is 1.89 Å. The Co(1)-O(4) bond length is 1.88 Å. There is one shorter (1.90 Å) and one longer (1.99 Å) Co(1)-O(2) bond length. 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 three equivalent Co(1)O5 trigonal bipyramids, corners with four equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one Co(1)O5 trigonal bipyramid. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.68 Å. The Si(1)-O(3) bond length is 1.62 Å. The Si(1)-O(4) bond length is 1.62 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Co(1), and one Si(1) atom to form corner-sharing OLi2CoSi trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Co(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one Si(1) atom.