V4Zn3(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(2)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,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. 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,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(10), one O(4), one O(7), and one O(9) atom to form ZnO5 trigonal bipyramids that share  a cornercorner with one Zn(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. In the second Zn site, Zn(2) 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, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 65°. 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(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 36-61°. 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(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 23-62°. 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(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and  a cornercorner with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 23-55°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Zn(1), one Zn(2), and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one Zn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Zn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(1), one Zn(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one Zn(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one V(1), one Zn(2), and one P(1) atom.
V4Zn3(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(2)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,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The V(1)-O(10) bond length is 2.06 Å. The V(1)-O(11) bond length is 1.93 Å. The V(1)-O(12) bond length is 2.08 Å. The V(1)-O(9) bond length is 2.05 Å. There is one shorter (2.08 Å) and one longer (2.10 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,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The V(2)-O(3) bond length is 1.97 Å. The V(2)-O(4) bond length is 2.10 Å. The V(2)-O(6) bond length is 1.95 Å. The V(2)-O(7) bond length is 2.06 Å. Both V(2)-O(5) bond lengths are 2.10 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(10), one O(4), one O(7), and one O(9) atom to form ZnO5 trigonal bipyramids that share  a cornercorner with one Zn(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. The Zn(1)-O(1) bond length is 1.99 Å. The Zn(1)-O(10) bond length is 2.06 Å. The Zn(1)-O(4) bond length is 2.11 Å. The Zn(1)-O(7) bond length is 2.13 Å. The Zn(1)-O(9) bond length is 2.11 Å. In the second Zn site, Zn(2) 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, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 65°. Both Zn(2)-O(1) bond lengths are 2.31 Å. Both Zn(2)-O(12) bond lengths are 2.28 Å. Both Zn(2)-O(2) bond lengths are 2.01 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(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 36-61°. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(7) bond length is 1.56 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(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 23-62°. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.53 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(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and  a cornercorner with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 23-55°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(2) bond length is 1.50 Å. The P(3)-O(5) bond length is 1.58 Å. The P(3)-O(8) bond length is 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Zn(1), one Zn(2), and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one Zn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Zn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(1), one Zn(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one Zn(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one V(1), one Zn(2), and one P(1) atom.