VCo2P2NO12 crystallizes in the orthorhombic Pmc2_1 space group. V(1) is bonded to one O(5), one O(6), one O(7), one O(9), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Co(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. Co(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CoO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. In the second P site, P(2) is bonded to one O(7), one O(9), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-59°. N(1) is bonded in a bent 120 degrees geometry to two equivalent O(4) atoms. There are nine inequivalent O sites. In the first O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one P(2) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Co(1) and one P(2) atom. In the third O site, O(2) is bonded in a trigonal planar geometry to two equivalent Co(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one N(1) atom. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Co(1) atoms. In the seventh O site, O(6) is bonded in a trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the eighth O site, O(7) is bonded in a linear geometry to one V(1) and one P(2) atom. In the ninth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.
VCo2P2NO12 crystallizes in the orthorhombic Pmc2_1 space group. V(1) is bonded to one O(5), one O(6), one O(7), one O(9), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Co(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The V(1)-O(5) bond length is 1.75 Å. The V(1)-O(6) bond length is 2.10 Å. The V(1)-O(7) bond length is 1.94 Å. The V(1)-O(9) bond length is 1.85 Å. Both V(1)-O(8) bond lengths are 1.91 Å. Co(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CoO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Co(1)-O(1) bond length is 1.95 Å. The Co(1)-O(2) bond length is 2.05 Å. The Co(1)-O(3) bond length is 2.11 Å. The Co(1)-O(4) bond length is 2.37 Å. The Co(1)-O(5) bond length is 2.21 Å. The Co(1)-O(6) bond length is 1.92 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. Both P(1)-O(8) bond lengths are 1.54 Å. In the second P site, P(2) is bonded to one O(7), one O(9), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-59°. The P(2)-O(7) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.60 Å. Both P(2)-O(1) bond lengths are 1.54 Å. N(1) is bonded in a bent 120 degrees geometry to two equivalent O(4) atoms. Both N(1)-O(4) bond lengths are 1.22 Å. There are nine inequivalent O sites. In the first O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one P(2) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Co(1) and one P(2) atom. In the third O site, O(2) is bonded in a trigonal planar geometry to two equivalent Co(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one N(1) atom. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Co(1) atoms. In the seventh O site, O(6) is bonded in a trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the eighth O site, O(7) is bonded in a linear geometry to one V(1) and one P(2) atom. In the ninth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.