V2NiO8 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms 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 16-33°. Ni(1) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra. There are five inequivalent O sites. In the first O site, O(4) is bonded in a linear geometry to one V(1) and one Ni(1) atom. In the second O site, O(5) is bonded in a single-bond geometry to one Ni(1) atom. In the third O site, O(1) is bonded in a single-bond geometry to one Ni(1) atom. In the fourth O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Ni(1) atom.
V2NiO8 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms 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 16-33°. The V(1)-O(3) bond length is 1.70 Å. The V(1)-O(4) bond length is 1.67 Å. There is one shorter (1.80 Å) and one longer (1.81 Å) V(1)-O(2) bond length. Ni(1) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra. The Ni(1)-O(1) bond length is 1.87 Å. The Ni(1)-O(5) bond length is 1.94 Å. Both Ni(1)-O(3) bond lengths are 2.04 Å. Both Ni(1)-O(4) bond lengths are 2.04 Å. There are five inequivalent O sites. In the first O site, O(4) is bonded in a linear geometry to one V(1) and one Ni(1) atom. In the second O site, O(5) is bonded in a single-bond geometry to one Ni(1) atom. In the third O site, O(1) is bonded in a single-bond geometry to one Ni(1) atom. In the fourth O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Ni(1) atom.