V2Co(PO5)2 crystallizes in the monoclinic P2_1/c space group. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted VO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-53°. Co(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted CoO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-50°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one Co(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one Co(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent V(1) and one Co(1) atom.
V2Co(PO5)2 crystallizes in the monoclinic P2_1/c space group. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted VO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-53°. The V(1)-O(1) bond length is 2.08 Å. The V(1)-O(2) bond length is 1.93 Å. The V(1)-O(3) bond length is 1.93 Å. The V(1)-O(4) bond length is 2.06 Å. There is one shorter (1.72 Å) and one longer (2.25 Å) V(1)-O(5) bond length. Co(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted CoO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Both Co(1)-O(1) bond lengths are 2.09 Å. Both Co(1)-O(4) bond lengths are 2.11 Å. Both Co(1)-O(5) bond lengths are 2.08 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-50°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.56 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one Co(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one Co(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent V(1) and one Co(1) atom.