V3(PO4)4 crystallizes in the monoclinic P2_1/c 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 two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. In the second V site, V(2) is bonded to one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-38°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with three equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 40°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom.
V3(PO4)4 crystallizes in the monoclinic P2_1/c 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 two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 1.94 Å. Both V(1)-O(2) bond lengths are 1.87 Å. Both V(1)-O(3) bond lengths are 1.96 Å. In the second V site, V(2) is bonded to one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The V(2)-O(4) bond length is 1.84 Å. The V(2)-O(5) bond length is 1.79 Å. The V(2)-O(6) bond length is 1.92 Å. The V(2)-O(7) bond length is 1.81 Å. The V(2)-O(8) bond length is 1.94 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-38°. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with three equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 40°. The P(2)-O(1) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom.