V4Zn(PO4)6 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(10), one O(11), one O(12), one O(9), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Zn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), one O(7), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. Zn(1) is bonded to two equivalent O(1), two equivalent O(12), and two equivalent O(2) atoms to form ZnO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-64°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Zn(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-57°. In the third P site, P(3) is bonded to one O(10), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-55°. There are twelve inequivalent O sites. In the first O site, O(12) is bonded in a distorted trigonal planar geometry to one V(1), one Zn(1), and one P(1) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(2) atom. In the third O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(3) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) atom. In the seventh O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the ninth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(3) atom. In the tenth O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the eleventh O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(3) atom. In the twelfth O site, O(11) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.
V4Zn(PO4)6 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(10), one O(11), one O(12), one O(9), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Zn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. The V(1)-O(10) bond length is 1.89 Å. The V(1)-O(11) bond length is 1.87 Å. The V(1)-O(12) bond length is 2.02 Å. The V(1)-O(9) bond length is 1.86 Å. There is one shorter (2.04 Å) and one longer (2.12 Å) V(1)-O(8) bond length. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), one O(7), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The V(2)-O(3) bond length is 1.97 Å. The V(2)-O(4) bond length is 1.89 Å. The V(2)-O(6) bond length is 1.88 Å. The V(2)-O(7) bond length is 1.93 Å. There is one shorter (2.06 Å) and one longer (2.18 Å) V(2)-O(5) bond length. Zn(1) is bonded to two equivalent O(1), two equivalent O(12), and two equivalent O(2) atoms to form ZnO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. Both Zn(1)-O(1) bond lengths are 2.06 Å. Both Zn(1)-O(12) bond lengths are 2.44 Å. Both Zn(1)-O(2) bond lengths are 2.05 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-64°. The P(1)-O(12) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(7) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.58 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Zn(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-57°. The P(2)-O(1) bond length is 1.50 Å. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(10), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-55°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(2) bond length is 1.49 Å. The P(3)-O(5) bond length is 1.58 Å. The P(3)-O(8) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(12) is bonded in a distorted trigonal planar geometry to one V(1), one Zn(1), and one P(1) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(2) atom. In the third O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(3) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) atom. In the seventh O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the ninth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(3) atom. In the tenth O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the eleventh O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(3) atom. In the twelfth O site, O(11) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.