LiVSiO4 is Corundum-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. V(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with four equivalent Si(1)O6 octahedra, and edges with two equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Si(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Si(1) atoms. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Si(1) atoms to form distorted OLiVSi2 trigonal pyramids that share corners with two equivalent O(2)LiVSi2 trigonal pyramids, corners with six equivalent O(3)LiV2Si trigonal pyramids, and edges with two equivalent O(3)LiV2Si trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Si(1) atom to form OLiV2Si trigonal pyramids that share corners with three equivalent O(2)LiVSi2 trigonal pyramids, corners with six equivalent O(3)LiV2Si trigonal pyramids,  an edgeedge with one O(3)LiV2Si trigonal pyramid, and  an edgeedge with one O(2)LiVSi2 trigonal pyramid.
LiVSiO4 is Corundum-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(2) bond length is 1.83 Å. Both Li(1)-O(3) bond lengths are 1.91 Å. V(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with four equivalent Si(1)O6 octahedra, and edges with two equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(1)-O(1) bond length is 2.07 Å. The V(1)-O(2) bond length is 2.08 Å. There are two shorter (2.03 Å) and two longer (2.08 Å) V(1)-O(3) bond lengths. Si(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both Si(1)-O(1) bond lengths are 1.88 Å. Both Si(1)-O(2) bond lengths are 1.80 Å. Both Si(1)-O(3) bond lengths are 1.79 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Si(1) atoms. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Si(1) atoms to form distorted OLiVSi2 trigonal pyramids that share corners with two equivalent O(2)LiVSi2 trigonal pyramids, corners with six equivalent O(3)LiV2Si trigonal pyramids, and edges with two equivalent O(3)LiV2Si trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Si(1) atom to form OLiV2Si trigonal pyramids that share corners with three equivalent O(2)LiVSi2 trigonal pyramids, corners with six equivalent O(3)LiV2Si trigonal pyramids,  an edgeedge with one O(3)LiV2Si trigonal pyramid, and  an edgeedge with one O(2)LiVSi2 trigonal pyramid.