V3(PO4)2 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(14), one O(16), one O(2), one O(4), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one V(5)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-65°. In the second V site, V(2) is bonded to one O(1), one O(11), one O(13), one O(15), one O(3), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(6)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one V(5)O6 octahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-66°. In the third V site, V(3) is bonded to one O(12), one O(14), one O(16), one O(2), one O(4), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-66°. In the fourth V site, V(4) is bonded to one O(12), one O(13), one O(16), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-66°. In the fifth V site, V(5) is bonded to one O(10), one O(11), one O(14), one O(15), one O(5), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-66°. In the sixth V site, V(6) is bonded to one O(1), one O(13), one O(15), one O(3), one O(5), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-64°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the second P site, P(2) is bonded to one O(10), one O(14), one O(2), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the third P site, P(3) is bonded to one O(11), one O(15), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the fourth P site, P(4) is bonded to one O(12), one O(16), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(6), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(6), and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(5), one V(6), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one P(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(4), one V(6), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one V(2), one V(4), one V(6), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), one V(5), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one V(2), one V(5), one V(6), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), one V(4), and one P(4) atom.
V3(PO4)2 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(14), one O(16), one O(2), one O(4), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one V(5)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-65°. The V(1)-O(10) bond length is 2.16 Å. The V(1)-O(14) bond length is 2.21 Å. The V(1)-O(16) bond length is 2.15 Å. The V(1)-O(2) bond length is 2.18 Å. The V(1)-O(4) bond length is 2.10 Å. The V(1)-O(6) bond length is 2.12 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(13), one O(15), one O(3), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(6)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one V(5)O6 octahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-66°. The V(2)-O(1) bond length is 2.10 Å. The V(2)-O(11) bond length is 2.16 Å. The V(2)-O(13) bond length is 2.16 Å. The V(2)-O(15) bond length is 2.22 Å. The V(2)-O(3) bond length is 2.17 Å. The V(2)-O(7) bond length is 2.12 Å. In the third V site, V(3) is bonded to one O(12), one O(14), one O(16), one O(2), one O(4), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-66°. The V(3)-O(12) bond length is 2.15 Å. The V(3)-O(14) bond length is 2.15 Å. The V(3)-O(16) bond length is 2.20 Å. The V(3)-O(2) bond length is 2.09 Å. The V(3)-O(4) bond length is 2.18 Å. The V(3)-O(8) bond length is 2.11 Å. In the fourth V site, V(4) is bonded to one O(12), one O(13), one O(16), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-66°. The V(4)-O(12) bond length is 2.15 Å. The V(4)-O(13) bond length is 2.16 Å. The V(4)-O(16) bond length is 2.15 Å. The V(4)-O(6) bond length is 2.15 Å. The V(4)-O(7) bond length is 2.15 Å. The V(4)-O(9) bond length is 2.17 Å. In the fifth V site, V(5) is bonded to one O(10), one O(11), one O(14), one O(15), one O(5), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-66°. The V(5)-O(10) bond length is 2.16 Å. The V(5)-O(11) bond length is 2.16 Å. The V(5)-O(14) bond length is 2.14 Å. The V(5)-O(15) bond length is 2.16 Å. The V(5)-O(5) bond length is 2.15 Å. The V(5)-O(8) bond length is 2.14 Å. In the sixth V site, V(6) is bonded to one O(1), one O(13), one O(15), one O(3), one O(5), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-64°. The V(6)-O(1) bond length is 2.19 Å. The V(6)-O(13) bond length is 2.21 Å. The V(6)-O(15) bond length is 2.17 Å. The V(6)-O(3) bond length is 2.10 Å. The V(6)-O(5) bond length is 2.12 Å. The V(6)-O(9) bond length is 2.16 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(13) bond length is 1.59 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(10), one O(14), one O(2), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The P(2)-O(10) bond length is 1.52 Å. The P(2)-O(14) bond length is 1.59 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(11), one O(15), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(15) bond length is 1.59 Å. The P(3)-O(3) bond length is 1.53 Å. The P(3)-O(8) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(12), one O(16), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. The P(4)-O(12) bond length is 1.52 Å. The P(4)-O(16) bond length is 1.59 Å. The P(4)-O(4) bond length is 1.53 Å. The P(4)-O(7) bond length is 1.54 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(6), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(6), and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(5), one V(6), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one P(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(4), one V(6), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one V(2), one V(4), one V(6), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), one V(5), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one V(2), one V(5), one V(6), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), one V(4), and one P(4) atom.