V3MnNi2(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 Ni(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. Mn(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form MnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ni(1)O6 octahedra. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted NiO6 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 Mn(1)O6 octahedra. In the second Ni site, Ni(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,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-49°. 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 Mn(1)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-51°. 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 Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(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 Ni(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 Mn(1), one Ni(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 Ni(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.
V3MnNi2(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 1.98 Å. All V(1)-O(8) bond lengths are 1.87 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 Ni(1)O6 octahedra. All V(2)-O(2) bond lengths are 1.99 Å. All V(2)-O(5) bond lengths are 1.89 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 1.88 Å. All V(3)-O(7) bond lengths are 2.00 Å. Mn(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form MnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ni(1)O6 octahedra. All Mn(1)-O(3) bond lengths are 1.94 Å. All Mn(1)-O(6) bond lengths are 2.06 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted NiO6 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 Mn(1)O6 octahedra. All Ni(1)-O(2) bond lengths are 2.11 Å. All Ni(1)-O(6) bond lengths are 2.10 Å. In the second Ni site, Ni(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. All Ni(2)-O(4) bond lengths are 2.13 Å. All Ni(2)-O(7) bond lengths are 2.12 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 Mn(1)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-49°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.49 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,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-51°. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.53 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 Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(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 Ni(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 Mn(1), one Ni(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 Ni(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.