V2NiO7 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-59°. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-51°. Ni(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms to form NiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Ni(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one Ni(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Ni(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one Ni(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Ni(1) atoms.
V2NiO7 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-59°. The V(1)-O(3) bond length is 1.66 Å. The V(1)-O(5) bond length is 1.81 Å. The V(1)-O(6) bond length is 1.78 Å. The V(1)-O(7) bond length is 1.73 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-51°. The V(2)-O(2) bond length is 1.69 Å. The V(2)-O(4) bond length is 1.69 Å. The V(2)-O(5) bond length is 1.79 Å. The V(2)-O(6) bond length is 1.80 Å. Ni(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms to form NiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The Ni(1)-O(1) bond length is 1.87 Å. The Ni(1)-O(2) bond length is 2.05 Å. The Ni(1)-O(3) bond length is 2.04 Å. The Ni(1)-O(4) bond length is 2.04 Å. There is one shorter (2.07 Å) and one longer (2.12 Å) Ni(1)-O(7) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Ni(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one Ni(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Ni(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one Ni(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Ni(1) atoms.