NaVSiO4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(2) atoms. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra and edges with two equivalent V(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 V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one V(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent V(1), and one Si(1) atom.
NaVSiO4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(2) atoms. Both Na(1)-O(1) bond lengths are 2.20 Å. There are two shorter (2.38 Å) and two longer (2.68 Å) Na(1)-O(2) bond lengths. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra and edges with two equivalent V(1)O6 octahedra. Both V(1)-O(1) bond lengths are 1.95 Å. All V(1)-O(2) bond lengths are 2.20 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 V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. Both Si(1)-O(1) bond lengths are 1.62 Å. Both Si(1)-O(2) bond lengths are 1.68 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one V(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent V(1), and one Si(1) atom.