V2(PO4)3 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(12), one O(9), and two equivalent O(8) atoms to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), one O(7), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-48°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-38°. In the third P site, P(3) is bonded to one O(10), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one P(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) 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(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(1) and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom.
V2(PO4)3 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(12), one O(9), and two equivalent O(8) atoms to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The V(1)-O(10) bond length is 1.79 Å. The V(1)-O(11) bond length is 1.77 Å. The V(1)-O(12) bond length is 1.88 Å. The V(1)-O(9) bond length is 1.89 Å. There is one shorter (2.08 Å) and one longer (2.20 Å) V(1)-O(8) bond length. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), one O(7), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The V(2)-O(3) bond length is 1.96 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(6) bond length is 1.90 Å. The V(2)-O(7) bond length is 1.91 Å. There is one shorter (2.05 Å) and one longer (2.15 Å) V(2)-O(5) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-48°. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(7) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.58 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-38°. The P(2)-O(1) bond length is 1.47 Å. The P(2)-O(11) bond length is 1.64 Å. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. The P(3)-O(10) bond length is 1.61 Å. The P(3)-O(2) bond length is 1.47 Å. The P(3)-O(5) bond length is 1.59 Å. The P(3)-O(8) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one P(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) 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(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(1) and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom.