ZnV2O6 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one Zn(2)O5 trigonal bipyramid, corners with two equivalent Zn(1)O5 trigonal bipyramids, and  an edgeedge with one Zn(2)O5 trigonal bipyramid. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(12), one O(3), one O(4), one O(7), and one O(8) atom. In the third V site, V(3) is bonded to one O(1), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form distorted VO6 octahedra that share  a cornercorner with one Zn(1)O5 trigonal bipyramid, corners with two equivalent Zn(2)O5 trigonal bipyramids, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(2), one O(5), and one O(6) atom. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(3), one O(6), one O(8), and one O(9) atom to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-57°. In the second Zn site, Zn(2) is bonded to one O(10), one O(2), one O(4), one O(5), and one O(7) atom to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one Zn(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(3), one V(4), and one Zn(2) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one Zn(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one Zn(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one Zn(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one Zn(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(3) and one Zn(1) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one V(1) and one Zn(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom.
ZnV2O6 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one Zn(2)O5 trigonal bipyramid, corners with two equivalent Zn(1)O5 trigonal bipyramids, and  an edgeedge with one Zn(2)O5 trigonal bipyramid. The V(1)-O(10) bond length is 1.70 Å. The V(1)-O(11) bond length is 2.25 Å. The V(1)-O(3) bond length is 1.84 Å. The V(1)-O(4) bond length is 2.08 Å. The V(1)-O(7) bond length is 2.00 Å. The V(1)-O(8) bond length is 1.79 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(12), one O(3), one O(4), one O(7), and one O(8) atom. The V(2)-O(12) bond length is 1.67 Å. The V(2)-O(3) bond length is 2.01 Å. The V(2)-O(4) bond length is 1.77 Å. The V(2)-O(7) bond length is 1.81 Å. The V(2)-O(8) bond length is 2.06 Å. In the third V site, V(3) is bonded to one O(1), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form distorted VO6 octahedra that share  a cornercorner with one Zn(1)O5 trigonal bipyramid, corners with two equivalent Zn(2)O5 trigonal bipyramids, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The V(3)-O(1) bond length is 2.08 Å. The V(3)-O(12) bond length is 2.25 Å. The V(3)-O(2) bond length is 1.83 Å. The V(3)-O(5) bond length is 1.80 Å. The V(3)-O(6) bond length is 2.01 Å. The V(3)-O(9) bond length is 1.70 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(2), one O(5), and one O(6) atom. The V(4)-O(1) bond length is 1.78 Å. The V(4)-O(11) bond length is 1.67 Å. The V(4)-O(2) bond length is 2.01 Å. The V(4)-O(5) bond length is 2.06 Å. The V(4)-O(6) bond length is 1.80 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(3), one O(6), one O(8), and one O(9) atom to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-57°. The Zn(1)-O(1) bond length is 2.12 Å. The Zn(1)-O(3) bond length is 2.02 Å. The Zn(1)-O(6) bond length is 2.13 Å. The Zn(1)-O(8) bond length is 2.04 Å. The Zn(1)-O(9) bond length is 2.00 Å. In the second Zn site, Zn(2) is bonded to one O(10), one O(2), one O(4), one O(5), and one O(7) atom to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-57°. The Zn(2)-O(10) bond length is 2.00 Å. The Zn(2)-O(2) bond length is 2.03 Å. The Zn(2)-O(4) bond length is 2.13 Å. The Zn(2)-O(5) bond length is 2.04 Å. The Zn(2)-O(7) bond length is 2.11 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one Zn(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(3), one V(4), and one Zn(2) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one Zn(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one Zn(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one Zn(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one Zn(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(3) and one Zn(1) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one V(1) and one Zn(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom.