V3Cr2Cu(PO4)6 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, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Cr(1)O6 octahedra. 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. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(2)O6 octahedra, and  a faceface with one Cu(1)O6 pentagonal pyramid. In the second Cr site, Cr(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. Cu(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted CuO6 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 Cr(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(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, and  a cornercorner with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 26-54°. 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,  a cornercorner with one Cr(1)O6 octahedra, and  a cornercorner with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 28-49°. 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 Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(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 Cr(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 Cr(1), one Cu(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 Cr(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.
V3Cr2Cu(PO4)6 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 2.02 Å. All V(1)-O(8) bond lengths are 1.89 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, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Cr(1)O6 octahedra. All V(2)-O(2) bond lengths are 2.09 Å. All V(2)-O(5) bond lengths are 1.97 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 1.90 Å. All V(3)-O(7) bond lengths are 2.04 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(2)O6 octahedra, and  a faceface with one Cu(1)O6 pentagonal pyramid. All Cr(1)-O(2) bond lengths are 2.12 Å. All Cr(1)-O(6) bond lengths are 2.06 Å. In the second Cr site, Cr(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. All Cr(2)-O(4) bond lengths are 2.19 Å. All Cr(2)-O(7) bond lengths are 2.17 Å. Cu(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted CuO6 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 Cr(1)O6 octahedra. All Cu(1)-O(3) bond lengths are 1.98 Å. All Cu(1)-O(6) bond lengths are 2.21 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,  a cornercorner with one Cr(1)O6 octahedra, and  a cornercorner with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 26-54°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.59 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,  a cornercorner with one Cr(1)O6 octahedra, and  a cornercorner with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 28-49°. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.58 Å. The P(2)-O(8) bond length is 1.55 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 Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(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 Cr(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 Cr(1), one Cu(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 Cr(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.