V3WCo2P6O24 crystallizes in the trigonal R3 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. W(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form WO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(6) atoms. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) 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 V(3)O6 octahedra, and  a cornercorner with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-47°. In the second P site, P(2) is bonded to one O(5), one O(6), 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 V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-45°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(2), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one Co(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one W(1), one Co(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(3), one Co(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.
V3WCo2P6O24 crystallizes in the trigonal R3 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All V(1)-O(4) bond lengths are 2.06 Å. All V(1)-O(8) bond lengths are 1.97 Å. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All V(2)-O(2) bond lengths are 2.05 Å. All V(2)-O(5) bond lengths are 1.94 Å. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All V(3)-O(1) bond lengths are 1.96 Å. All V(3)-O(7) bond lengths are 2.04 Å. W(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form WO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All W(1)-O(3) bond lengths are 1.96 Å. All W(1)-O(6) bond lengths are 2.02 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(6) atoms. All Co(1)-O(2) bond lengths are 2.20 Å. All Co(1)-O(6) bond lengths are 2.39 Å. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. All Co(2)-O(4) bond lengths are 2.25 Å. All Co(2)-O(7) bond lengths are 2.26 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) 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 V(3)O6 octahedra, and  a cornercorner with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-47°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(5), one O(6), 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 V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-45°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.52 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(3) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(2), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one Co(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one W(1), one Co(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(3), one Co(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.