V3Ni(PO4)4 crystallizes in the monoclinic Pm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with four equivalent V(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the second V site, V(2) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the third V site, V(3) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. Ni(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted NiO6 octahedra that share corners with four equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-50°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-60°. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-58°. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. There are twelve 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 distorted trigonal planar 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 V(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Ni(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(2), one Ni(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ni(1) and one P(4) atom.
V3Ni(PO4)4 crystallizes in the monoclinic Pm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with four equivalent V(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The V(1)-O(3) bond length is 1.95 Å. The V(1)-O(7) bond length is 1.99 Å. Both V(1)-O(11) bond lengths are 2.08 Å. Both V(1)-O(5) bond lengths are 2.12 Å. In the second V site, V(2) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-50°. The V(2)-O(10) bond length is 1.94 Å. The V(2)-O(6) bond length is 1.95 Å. Both V(2)-O(2) bond lengths are 2.08 Å. Both V(2)-O(8) bond lengths are 1.94 Å. In the third V site, V(3) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The V(3)-O(1) bond length is 1.98 Å. The V(3)-O(9) bond length is 1.99 Å. Both V(3)-O(11) bond lengths are 2.09 Å. Both V(3)-O(5) bond lengths are 2.11 Å. Ni(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted NiO6 octahedra that share corners with four equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Ni(1)-O(12) bond length is 1.96 Å. The Ni(1)-O(4) bond length is 1.95 Å. Both Ni(1)-O(2) bond lengths are 2.10 Å. Both Ni(1)-O(8) bond lengths are 2.29 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-60°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(10) bond length is 1.54 Å. Both P(1)-O(2) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-58°. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.52 Å. Both P(2)-O(5) bond lengths are 1.58 Å. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. The P(3)-O(4) bond length is 1.50 Å. The P(3)-O(7) bond length is 1.52 Å. Both P(3)-O(8) bond lengths are 1.61 Å. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. The P(4)-O(12) bond length is 1.50 Å. The P(4)-O(3) bond length is 1.52 Å. Both P(4)-O(11) bond lengths are 1.60 Å. There are twelve 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 distorted trigonal planar 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 V(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Ni(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(2), one Ni(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ni(1) and one P(4) atom.