V(PO3)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(1), one O(10), one O(11), one O(12), one O(18), and one O(5) atom to form VO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. In the second V site, V(2) is bonded to one O(10), one O(12), one O(14), one O(16), one O(17), and one O(4) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(5)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(16), one O(17), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-51°. In the second P site, P(2) is bonded to one O(10), one O(18), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the third P site, P(3) is bonded to one O(1), one O(14), one O(2), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-44°. In the fourth P site, P(4) is bonded to one O(13), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. In the fifth P site, P(5) is bonded to one O(12), one O(13), one O(2), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-57°. In the sixth P site, P(6) is bonded to one O(11), one O(15), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 16°. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one P(3) and one P(5) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one P(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(3) and one P(6) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(1) and one P(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(1) and one P(6) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one P(4) and one P(5) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one P(6) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one V(2) and one P(1) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom.
V(PO3)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(1), one O(10), one O(11), one O(12), one O(18), and one O(5) atom to form VO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(10) bond length is 2.24 Å. The V(1)-O(11) bond length is 1.96 Å. The V(1)-O(12) bond length is 2.22 Å. The V(1)-O(18) bond length is 2.07 Å. The V(1)-O(5) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(10), one O(12), one O(14), one O(16), one O(17), and one O(4) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(5)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The V(2)-O(10) bond length is 2.16 Å. The V(2)-O(12) bond length is 2.15 Å. The V(2)-O(14) bond length is 2.00 Å. The V(2)-O(16) bond length is 2.00 Å. The V(2)-O(17) bond length is 2.01 Å. The V(2)-O(4) bond length is 2.01 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(16), one O(17), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-51°. The P(1)-O(16) bond length is 1.50 Å. The P(1)-O(17) bond length is 1.50 Å. The P(1)-O(8) bond length is 1.58 Å. The P(1)-O(9) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(10), one O(18), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(18) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.58 Å. The P(2)-O(9) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(1), one O(14), one O(2), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-44°. The P(3)-O(1) bond length is 1.51 Å. The P(3)-O(14) bond length is 1.51 Å. The P(3)-O(2) bond length is 1.61 Å. The P(3)-O(7) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(13), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. The P(4)-O(13) bond length is 1.64 Å. The P(4)-O(3) bond length is 1.66 Å. The P(4)-O(5) bond length is 1.52 Å. The P(4)-O(6) bond length is 1.46 Å. In the fifth P site, P(5) is bonded to one O(12), one O(13), one O(2), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-57°. The P(5)-O(12) bond length is 1.54 Å. The P(5)-O(13) bond length is 1.57 Å. The P(5)-O(2) bond length is 1.59 Å. The P(5)-O(4) bond length is 1.50 Å. In the sixth P site, P(6) is bonded to one O(11), one O(15), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 16°. The P(6)-O(11) bond length is 1.52 Å. The P(6)-O(15) bond length is 1.45 Å. The P(6)-O(7) bond length is 1.66 Å. The P(6)-O(8) bond length is 1.66 Å. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one P(3) and one P(5) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one P(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(3) and one P(6) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(1) and one P(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(1) and one P(6) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one P(4) and one P(5) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one P(6) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one V(2) and one P(1) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom.