V5Sb(PO4)6 crystallizes in the trigonal R3 space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(4)O6 octahedra, and  a faceface with one Sb(1)O6 pentagonal pyramid. In the second V site, V(2) 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 third V site, V(3) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. In the fourth V site, V(4) 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, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. In the fifth V site, V(5) 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. Sb(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted SbO6 pentagonal pyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. 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(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 19-53°. 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(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 27-50°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(5) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Sb(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(4) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Sb(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 V(5), 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(2) atom.
V5Sb(PO4)6 crystallizes in the trigonal R3 space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(4)O6 octahedra, and  a faceface with one Sb(1)O6 pentagonal pyramid. All V(1)-O(2) bond lengths are 2.10 Å. All V(1)-O(6) bond lengths are 2.16 Å. In the second V site, V(2) 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(2)-O(4) bond lengths are 2.01 Å. All V(2)-O(8) bond lengths are 1.90 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. All V(3)-O(4) bond lengths are 2.22 Å. All V(3)-O(7) bond lengths are 2.22 Å. In the fourth V site, V(4) 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, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. All V(4)-O(2) bond lengths are 2.13 Å. All V(4)-O(5) bond lengths are 1.98 Å. In the fifth V site, V(5) 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(5)-O(1) bond lengths are 2.00 Å. All V(5)-O(7) bond lengths are 2.08 Å. Sb(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted SbO6 pentagonal pyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. All Sb(1)-O(3) bond lengths are 2.16 Å. All Sb(1)-O(6) bond lengths are 2.37 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(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 19-53°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.57 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(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 27-50°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 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(5) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Sb(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(4) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Sb(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 V(5), 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(2) atom.