Ni2V2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Ni(2)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-58°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-62°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form NiO6 octahedra that share corners with three equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Ni(2)O6 octahedra. In the second Ni site, Ni(2) is bonded to one O(2), one O(4), one O(6), one O(7), and two equivalent O(1) atoms to form NiO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Ni(1) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one Ni(1), and one Ni(2) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent Ni(2) atoms. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Ni(1) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom.
Ni2V2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Ni(2)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-58°. The V(1)-O(2) bond length is 1.71 Å. The V(1)-O(4) bond length is 1.71 Å. The V(1)-O(5) bond length is 1.84 Å. The V(1)-O(7) bond length is 1.70 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-62°. The V(2)-O(1) bond length is 1.72 Å. The V(2)-O(3) bond length is 1.65 Å. The V(2)-O(5) bond length is 1.85 Å. The V(2)-O(6) bond length is 1.73 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form NiO6 octahedra that share corners with three equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Ni(2)O6 octahedra. The Ni(1)-O(2) bond length is 2.00 Å. The Ni(1)-O(3) bond length is 1.97 Å. The Ni(1)-O(4) bond length is 2.03 Å. The Ni(1)-O(5) bond length is 2.09 Å. The Ni(1)-O(6) bond length is 2.02 Å. The Ni(1)-O(7) bond length is 2.07 Å. In the second Ni site, Ni(2) is bonded to one O(2), one O(4), one O(6), one O(7), and two equivalent O(1) atoms to form NiO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The Ni(2)-O(2) bond length is 2.03 Å. The Ni(2)-O(4) bond length is 2.02 Å. The Ni(2)-O(6) bond length is 2.03 Å. The Ni(2)-O(7) bond length is 2.04 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) Ni(2)-O(1) bond length. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Ni(1) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one Ni(1), and one Ni(2) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent Ni(2) atoms. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Ni(1) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom.