Zr7VO16 crystallizes in the monoclinic Cm space group. There are five inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(5), two equivalent O(12), and two equivalent O(9) atoms. In the second Zr site, Zr(2) is bonded in a 8-coordinate geometry to one O(4), one O(5), one O(6), one O(7), two equivalent O(10), and two equivalent O(11) atoms. In the third Zr site, Zr(3) is bonded in a distorted body-centered cubic geometry to one O(2), one O(4), one O(7), one O(8), two equivalent O(12), and two equivalent O(9) atoms. In the fourth Zr site, Zr(4) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(4), one O(5), and one O(9) atom. In the fifth Zr site, Zr(5) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(12), one O(3), one O(6), one O(7), one O(8), and one O(9) atom. V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(8), and two equivalent O(11) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Zr(1), two equivalent Zr(4), and one V(1) atom. In the second O site, O(2) is bonded to one Zr(3), two equivalent Zr(4), and one V(1) atom to form distorted OZr3V tetrahedra that share  a cornercorner with one O(3)Zr3V tetrahedra,  a cornercorner with one O(7)Zr4 tetrahedra, corners with two equivalent O(5)Zr4 tetrahedra, corners with three equivalent O(4)Zr4 tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(8)Zr3V tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the third O site, O(3) is bonded to one Zr(1), two equivalent Zr(5), and one V(1) atom to form distorted OZr3V tetrahedra that share  a cornercorner with one O(2)Zr3V tetrahedra,  a cornercorner with one O(5)Zr4 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with three equivalent O(8)Zr3V tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the fourth O site, O(4) is bonded to one Zr(2), one Zr(3), and two equivalent Zr(4) atoms to form distorted OZr4 tetrahedra that share  a cornercorner with one O(8)Zr3V tetrahedra,  a cornercorner with one O(5)Zr4 tetrahedra, corners with three equivalent O(2)Zr3V tetrahedra, corners with four equivalent O(12)Zr4 tetrahedra,  an edgeedge with one O(5)Zr4 tetrahedra,  an edgeedge with one O(7)Zr4 tetrahedra, and edges with two equivalent O(9)Zr4 tetrahedra. In the fifth O site, O(5) is bonded to one Zr(1), one Zr(2), and two equivalent Zr(4) atoms to form distorted OZr4 tetrahedra that share  a cornercorner with one O(3)Zr3V tetrahedra,  a cornercorner with one O(4)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 tetrahedra, corners with two equivalent O(2)Zr3V tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(4)Zr4 tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zr(2) and two equivalent Zr(5) atoms. In the seventh O site, O(7) is bonded to one Zr(2), one Zr(3), and two equivalent Zr(5) atoms to form distorted OZr4 tetrahedra that share  a cornercorner with one O(2)Zr3V tetrahedra,  a cornercorner with one O(8)Zr3V tetrahedra,  a cornercorner with one O(5)Zr4 tetrahedra, corners with two equivalent O(3)Zr3V tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(8)Zr3V tetrahedra,  an edgeedge with one O(4)Zr4 tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the eighth O site, O(8) is bonded to one Zr(3), two equivalent Zr(5), and one V(1) atom to form distorted OZr3V tetrahedra that share  a cornercorner with one O(4)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 tetrahedra, corners with three equivalent O(3)Zr3V tetrahedra, corners with four equivalent O(12)Zr4 tetrahedra,  an edgeedge with one O(2)Zr3V tetrahedra,  an edgeedge with one O(7)Zr4 tetrahedra, and edges with two equivalent O(9)Zr4 tetrahedra. In the ninth O site, O(9) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Zr(5) atom to form distorted OZr4 tetrahedra that share corners with two equivalent O(2)Zr3V tetrahedra, corners with two equivalent O(3)Zr3V tetrahedra, corners with two equivalent O(5)Zr4 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with two equivalent O(9)Zr4 tetrahedra, corners with four equivalent O(12)Zr4 tetrahedra,  an edgeedge with one O(8)Zr3V tetrahedra,  an edgeedge with one O(12)Zr4 tetrahedra, and  an edgeedge with one O(4)Zr4 tetrahedra. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Zr(2), one Zr(4), and one Zr(5) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Zr(2), one Zr(4), one Zr(5), and one V(1) atom. In the twelfth O site, O(12) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Zr(5) atom to form distorted OZr4 tetrahedra that share corners with two equivalent O(8)Zr3V tetrahedra, corners with two equivalent O(12)Zr4 tetrahedra, corners with two equivalent O(4)Zr4 tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(2)Zr3V tetrahedra,  an edgeedge with one O(3)Zr3V tetrahedra,  an edgeedge with one O(5)Zr4 tetrahedra,  an edgeedge with one O(7)Zr4 tetrahedra, and  an edgeedge with one O(9)Zr4 tetrahedra.
Zr7VO16 crystallizes in the monoclinic Cm space group. There are five inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(5), two equivalent O(12), and two equivalent O(9) atoms. The Zr(1)-O(1) bond length is 2.27 Å. The Zr(1)-O(3) bond length is 2.10 Å. The Zr(1)-O(5) bond length is 2.11 Å. Both Zr(1)-O(12) bond lengths are 2.40 Å. Both Zr(1)-O(9) bond lengths are 2.10 Å. In the second Zr site, Zr(2) is bonded in a 8-coordinate geometry to one O(4), one O(5), one O(6), one O(7), two equivalent O(10), and two equivalent O(11) atoms. The Zr(2)-O(4) bond length is 2.57 Å. The Zr(2)-O(5) bond length is 2.10 Å. The Zr(2)-O(6) bond length is 2.26 Å. The Zr(2)-O(7) bond length is 2.13 Å. Both Zr(2)-O(10) bond lengths are 2.24 Å. Both Zr(2)-O(11) bond lengths are 2.19 Å. In the third Zr site, Zr(3) is bonded in a distorted body-centered cubic geometry to one O(2), one O(4), one O(7), one O(8), two equivalent O(12), and two equivalent O(9) atoms. The Zr(3)-O(2) bond length is 2.15 Å. The Zr(3)-O(4) bond length is 2.40 Å. The Zr(3)-O(7) bond length is 2.07 Å. The Zr(3)-O(8) bond length is 2.47 Å. Both Zr(3)-O(12) bond lengths are 2.47 Å. Both Zr(3)-O(9) bond lengths are 2.10 Å. In the fourth Zr site, Zr(4) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(4), one O(5), and one O(9) atom. The Zr(4)-O(1) bond length is 2.09 Å. The Zr(4)-O(10) bond length is 2.03 Å. The Zr(4)-O(11) bond length is 2.68 Å. The Zr(4)-O(12) bond length is 2.11 Å. The Zr(4)-O(2) bond length is 2.50 Å. The Zr(4)-O(4) bond length is 2.09 Å. The Zr(4)-O(5) bond length is 2.45 Å. The Zr(4)-O(9) bond length is 2.35 Å. In the fifth Zr site, Zr(5) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(12), one O(3), one O(6), one O(7), one O(8), and one O(9) atom. The Zr(5)-O(10) bond length is 2.05 Å. The Zr(5)-O(11) bond length is 2.41 Å. The Zr(5)-O(12) bond length is 2.08 Å. The Zr(5)-O(3) bond length is 2.49 Å. The Zr(5)-O(6) bond length is 2.08 Å. The Zr(5)-O(7) bond length is 2.44 Å. The Zr(5)-O(8) bond length is 2.09 Å. The Zr(5)-O(9) bond length is 2.56 Å. V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(8), and two equivalent O(11) atoms. The V(1)-O(1) bond length is 2.59 Å. The V(1)-O(2) bond length is 1.96 Å. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(8) bond length is 2.14 Å. Both V(1)-O(11) bond lengths are 1.85 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Zr(1), two equivalent Zr(4), and one V(1) atom. In the second O site, O(2) is bonded to one Zr(3), two equivalent Zr(4), and one V(1) atom to form distorted OZr3V tetrahedra that share  a cornercorner with one O(3)Zr3V tetrahedra,  a cornercorner with one O(7)Zr4 tetrahedra, corners with two equivalent O(5)Zr4 tetrahedra, corners with three equivalent O(4)Zr4 tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(8)Zr3V tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the third O site, O(3) is bonded to one Zr(1), two equivalent Zr(5), and one V(1) atom to form distorted OZr3V tetrahedra that share  a cornercorner with one O(2)Zr3V tetrahedra,  a cornercorner with one O(5)Zr4 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with three equivalent O(8)Zr3V tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the fourth O site, O(4) is bonded to one Zr(2), one Zr(3), and two equivalent Zr(4) atoms to form distorted OZr4 tetrahedra that share  a cornercorner with one O(8)Zr3V tetrahedra,  a cornercorner with one O(5)Zr4 tetrahedra, corners with three equivalent O(2)Zr3V tetrahedra, corners with four equivalent O(12)Zr4 tetrahedra,  an edgeedge with one O(5)Zr4 tetrahedra,  an edgeedge with one O(7)Zr4 tetrahedra, and edges with two equivalent O(9)Zr4 tetrahedra. In the fifth O site, O(5) is bonded to one Zr(1), one Zr(2), and two equivalent Zr(4) atoms to form distorted OZr4 tetrahedra that share  a cornercorner with one O(3)Zr3V tetrahedra,  a cornercorner with one O(4)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 tetrahedra, corners with two equivalent O(2)Zr3V tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(4)Zr4 tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zr(2) and two equivalent Zr(5) atoms. In the seventh O site, O(7) is bonded to one Zr(2), one Zr(3), and two equivalent Zr(5) atoms to form distorted OZr4 tetrahedra that share  a cornercorner with one O(2)Zr3V tetrahedra,  a cornercorner with one O(8)Zr3V tetrahedra,  a cornercorner with one O(5)Zr4 tetrahedra, corners with two equivalent O(3)Zr3V tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(8)Zr3V tetrahedra,  an edgeedge with one O(4)Zr4 tetrahedra, and edges with two equivalent O(12)Zr4 tetrahedra. In the eighth O site, O(8) is bonded to one Zr(3), two equivalent Zr(5), and one V(1) atom to form distorted OZr3V tetrahedra that share  a cornercorner with one O(4)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 tetrahedra, corners with three equivalent O(3)Zr3V tetrahedra, corners with four equivalent O(12)Zr4 tetrahedra,  an edgeedge with one O(2)Zr3V tetrahedra,  an edgeedge with one O(7)Zr4 tetrahedra, and edges with two equivalent O(9)Zr4 tetrahedra. In the ninth O site, O(9) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Zr(5) atom to form distorted OZr4 tetrahedra that share corners with two equivalent O(2)Zr3V tetrahedra, corners with two equivalent O(3)Zr3V tetrahedra, corners with two equivalent O(5)Zr4 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with two equivalent O(9)Zr4 tetrahedra, corners with four equivalent O(12)Zr4 tetrahedra,  an edgeedge with one O(8)Zr3V tetrahedra,  an edgeedge with one O(12)Zr4 tetrahedra, and  an edgeedge with one O(4)Zr4 tetrahedra. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Zr(2), one Zr(4), and one Zr(5) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Zr(2), one Zr(4), one Zr(5), and one V(1) atom. In the twelfth O site, O(12) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Zr(5) atom to form distorted OZr4 tetrahedra that share corners with two equivalent O(8)Zr3V tetrahedra, corners with two equivalent O(12)Zr4 tetrahedra, corners with two equivalent O(4)Zr4 tetrahedra, corners with four equivalent O(9)Zr4 tetrahedra,  an edgeedge with one O(2)Zr3V tetrahedra,  an edgeedge with one O(3)Zr3V tetrahedra,  an edgeedge with one O(5)Zr4 tetrahedra,  an edgeedge with one O(7)Zr4 tetrahedra, and  an edgeedge with one O(9)Zr4 tetrahedra.