V2CoO8 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-27°. Co(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form CoO6 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 single-bond geometry to one Co(1) atom. In the second O site, O(5) is bonded in a single-bond geometry to one Co(1) atom. In the third O site, O(1) is bonded in a linear geometry to one V(1) and one Co(1) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
V2CoO8 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-27°. The V(1)-O(1) bond length is 1.68 Å. The V(1)-O(2) bond length is 1.70 Å. There is one shorter (1.79 Å) and one longer (1.81 Å) V(1)-O(3) bond length. Co(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form CoO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra. The Co(1)-O(4) bond length is 1.73 Å. The Co(1)-O(5) bond length is 1.73 Å. Both Co(1)-O(1) bond lengths are 2.01 Å. Both Co(1)-O(2) bond lengths are 1.94 Å. There are five inequivalent O sites. In the first O site, O(4) is bonded in a single-bond geometry to one Co(1) atom. In the second O site, O(5) is bonded in a single-bond geometry to one Co(1) atom. In the third O site, O(1) is bonded in a linear geometry to one V(1) and one Co(1) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.