NaV3(PO4)3 crystallizes in the orthorhombic Imma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. 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(4) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the second P site, P(2) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent V(1), and one P(2) atom. In the second O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(1) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the fourth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and one P(2) atom.
NaV3(PO4)3 crystallizes in the orthorhombic Imma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. Both Na(1)-O(3) bond lengths are 2.64 Å. Both Na(1)-O(4) bond lengths are 2.70 Å. All Na(1)-O(2) bond lengths are 2.77 Å. 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(4) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. Both V(1)-O(1) bond lengths are 2.11 Å. Both V(1)-O(2) bond lengths are 2.10 Å. Both V(1)-O(4) bond lengths are 2.10 Å. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. Both V(2)-O(3) bond lengths are 2.10 Å. All V(2)-O(1) bond lengths are 2.02 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. Both P(1)-O(1) bond lengths are 1.60 Å. Both P(1)-O(2) bond lengths are 1.52 Å. In the second P site, P(2) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. Both P(2)-O(3) bond lengths are 1.53 Å. Both P(2)-O(4) bond lengths are 1.58 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent V(1), and one P(2) atom. In the second O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(1) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the fourth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and one P(2) atom.