VNi3Sn2(PO4)6 crystallizes in the trigonal R3 space group. V(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted 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 Sn(1)O6 octahedra. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form distorted NiO6 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 Sn(2)O6 octahedra. In the second Ni site, Ni(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Sn(1)O6 octahedra. In the third Ni site, Ni(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Sn(2)O6 octahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted SnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one Ni(2)O6 octahedra. In the second Sn site, Sn(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted SnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ni(3)O6 octahedra, and  a faceface with one Ni(1)O6 pentagonal pyramid. 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 Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Sn(1)O6 octahedra,  a cornercorner with one Sn(2)O6 octahedra, and  a cornercorner with one Ni(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 29-51°. 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 Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Sn(1)O6 octahedra,  a cornercorner with one Sn(2)O6 octahedra, and  a cornercorner with one Ni(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 36-52°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ni(3) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ni(2), one Sn(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ni(1), one Sn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Sn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ni(3), one Sn(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(2) atom.
VNi3Sn2(PO4)6 crystallizes in the trigonal R3 space group. V(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted 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 Sn(1)O6 octahedra. All V(1)-O(3) bond lengths are 1.87 Å. All V(1)-O(6) bond lengths are 2.06 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form distorted NiO6 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 Sn(2)O6 octahedra. All Ni(1)-O(4) bond lengths are 2.20 Å. All Ni(1)-O(8) bond lengths are 1.98 Å. In the second Ni site, Ni(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Sn(1)O6 octahedra. All Ni(2)-O(2) bond lengths are 2.14 Å. All Ni(2)-O(5) bond lengths are 1.95 Å. In the third Ni site, Ni(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Sn(2)O6 octahedra. All Ni(3)-O(1) bond lengths are 1.96 Å. All Ni(3)-O(7) bond lengths are 2.11 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted SnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one Ni(2)O6 octahedra. All Sn(1)-O(2) bond lengths are 2.12 Å. All Sn(1)-O(6) bond lengths are 2.17 Å. In the second Sn site, Sn(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted SnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ni(3)O6 octahedra, and  a faceface with one Ni(1)O6 pentagonal pyramid. All Sn(2)-O(4) bond lengths are 2.11 Å. All Sn(2)-O(7) bond lengths are 2.11 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 Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Sn(1)O6 octahedra,  a cornercorner with one Sn(2)O6 octahedra, and  a cornercorner with one Ni(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 29-51°. The P(1)-O(1) bond length is 1.48 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.56 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 Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Sn(1)O6 octahedra,  a cornercorner with one Sn(2)O6 octahedra, and  a cornercorner with one Ni(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 36-52°. The P(2)-O(5) bond length is 1.49 Å. The P(2)-O(6) bond length is 1.64 Å. The P(2)-O(7) bond length is 1.59 Å. The P(2)-O(8) bond length is 1.50 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ni(3) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ni(2), one Sn(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ni(1), one Sn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Sn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ni(3), one Sn(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(2) atom.