V2SiO4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-63°. In the second V site, V(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-63°. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Si(1) atom. In the second O site, O(2) is bonded to one V(2), two equivalent V(1), and one Si(1) atom to form distorted corner-sharing OV3Si trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Si(1) atom.
V2SiO4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-63°. Both V(1)-O(1) bond lengths are 2.14 Å. Both V(1)-O(2) bond lengths are 2.15 Å. Both V(1)-O(3) bond lengths are 2.18 Å. In the second V site, V(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-63°. The V(2)-O(1) bond length is 2.12 Å. The V(2)-O(2) bond length is 2.18 Å. There are two shorter (2.15 Å) and two longer (2.23 Å) V(2)-O(3) bond lengths. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.62 Å. Both Si(1)-O(3) bond lengths are 1.65 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 V(2), two equivalent V(1), and one Si(1) atom. In the second O site, O(2) is bonded to one V(2), two equivalent V(1), and one Si(1) atom to form distorted corner-sharing OV3Si trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Si(1) atom.