NiV2O6 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(7), and two equivalent O(2) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(9), and two equivalent O(3) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(4), one O(5), one O(7), one O(8), and two equivalent O(9) atoms to form NiO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Ni(2)O6 octahedra. In the second Ni site, Ni(2) is bonded to two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra and edges with two equivalent Ni(1)O6 octahedra. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(2), one V(3), and one Ni(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one Ni(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one Ni(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Ni(1), and one Ni(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(3) and two equivalent Ni(1) atoms.
NiV2O6 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The V(1)-O(1) bond length is 1.70 Å. The V(1)-O(2) bond length is 1.77 Å. The V(1)-O(3) bond length is 1.77 Å. The V(1)-O(8) bond length is 1.70 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(7), and two equivalent O(2) atoms. The V(2)-O(1) bond length is 2.26 Å. The V(2)-O(4) bond length is 1.86 Å. The V(2)-O(6) bond length is 1.64 Å. The V(2)-O(7) bond length is 1.72 Å. There is one shorter (1.99 Å) and one longer (2.16 Å) V(2)-O(2) bond length. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(9), and two equivalent O(3) atoms. The V(3)-O(1) bond length is 2.27 Å. The V(3)-O(4) bond length is 1.88 Å. The V(3)-O(5) bond length is 1.63 Å. The V(3)-O(9) bond length is 1.72 Å. There is one shorter (1.99 Å) and one longer (2.14 Å) V(3)-O(3) bond length. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(4), one O(5), one O(7), one O(8), and two equivalent O(9) atoms to form NiO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Ni(2)O6 octahedra. The Ni(1)-O(4) bond length is 2.07 Å. The Ni(1)-O(5) bond length is 1.98 Å. The Ni(1)-O(7) bond length is 1.98 Å. The Ni(1)-O(8) bond length is 2.04 Å. There is one shorter (1.99 Å) and one longer (2.00 Å) Ni(1)-O(9) bond length. In the second Ni site, Ni(2) is bonded to two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra and edges with two equivalent Ni(1)O6 octahedra. Both Ni(2)-O(6) bond lengths are 1.93 Å. Both Ni(2)-O(7) bond lengths are 1.99 Å. Both Ni(2)-O(8) bond lengths are 2.01 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(2), one V(3), and one Ni(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one Ni(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one Ni(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Ni(1), and one Ni(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(3) and two equivalent Ni(1) atoms.