Ni5Sb(PO4)6 crystallizes in the trigonal R3 space group. There are five 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 Ni(4)O6 octahedra, and  a faceface with one Sb(1)O6 octahedra. In the second Ni site, Ni(2) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form 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 Ni(3)O6 octahedra. In the third Ni site, Ni(3) is bonded to three equivalent O(4) 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,  a faceface with one Ni(2)O6 octahedra, and  a faceface with one Ni(5)O6 octahedra. In the fourth Ni site, Ni(4) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form 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 Ni(1)O6 octahedra. In the fifth Ni site, Ni(5) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form 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 Ni(3)O6 octahedra. Sb(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form SbO6 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 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 Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-52°. 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 Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-51°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ni(5) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(4), and one P(1) atom. In the third O site, O(3) is bonded in a 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 Ni(2), one Ni(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ni(4) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ni(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 Ni(3), one Ni(5), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(2) atom.
Ni5Sb(PO4)6 crystallizes in the trigonal R3 space group. There are five 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 Ni(4)O6 octahedra, and  a faceface with one Sb(1)O6 octahedra. All Ni(1)-O(2) bond lengths are 2.09 Å. All Ni(1)-O(6) bond lengths are 2.24 Å. In the second Ni site, Ni(2) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form 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 Ni(3)O6 octahedra. All Ni(2)-O(4) bond lengths are 2.08 Å. All Ni(2)-O(8) bond lengths are 2.00 Å. In the third Ni site, Ni(3) is bonded to three equivalent O(4) 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,  a faceface with one Ni(2)O6 octahedra, and  a faceface with one Ni(5)O6 octahedra. All Ni(3)-O(4) bond lengths are 2.13 Å. All Ni(3)-O(7) bond lengths are 2.14 Å. In the fourth Ni site, Ni(4) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form 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 Ni(1)O6 octahedra. All Ni(4)-O(2) bond lengths are 2.08 Å. All Ni(4)-O(5) bond lengths are 1.97 Å. In the fifth Ni site, Ni(5) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form 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 Ni(3)O6 octahedra. All Ni(5)-O(1) bond lengths are 1.98 Å. All Ni(5)-O(7) bond lengths are 2.05 Å. Sb(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form SbO6 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 Sb(1)-O(3) bond lengths are 1.95 Å. All Sb(1)-O(6) bond lengths are 2.03 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 Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-52°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.58 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 Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra, and  a cornercorner with one Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-51°. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.63 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.51 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(5) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(4), and one P(1) atom. In the third O site, O(3) is bonded in a 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 Ni(2), one Ni(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ni(4) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ni(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 Ni(3), one Ni(5), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(2) atom.