Zn3(OH)2V2O7O2 crystallizes in the monoclinic C2 space group. The structure consists of four water atoms inside a Zn3(OH)2V2O7 framework. In the Zn3(OH)2V2O7 framework, V(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form VO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with four equivalent Zn(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form ZnO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra and edges with four equivalent Zn(2)O6 octahedra. In the second Zn site, Zn(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form ZnO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with two equivalent Zn(2)O6 octahedra. H(1) is bonded in a single-bond geometry to one O(4) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Zn(2) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one Zn(1), and one Zn(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Zn(1), and one Zn(2) atom. In the fourth O site, O(4) is bonded to one Zn(1), two equivalent Zn(2), and one H(1) atom to form distorted corner-sharing OZn3H tetrahedra. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent V(1) atoms.
Zn3(OH)2V2O7O2 crystallizes in the monoclinic C2 space group. The structure consists of four water atoms inside a Zn3(OH)2V2O7 framework. In the Zn3(OH)2V2O7 framework, V(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form VO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with four equivalent Zn(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. The V(1)-O(1) bond length is 1.74 Å. The V(1)-O(2) bond length is 1.74 Å. The V(1)-O(3) bond length is 1.74 Å. The V(1)-O(5) bond length is 1.80 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form ZnO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra and edges with four equivalent Zn(2)O6 octahedra. Both Zn(1)-O(2) bond lengths are 2.20 Å. Both Zn(1)-O(3) bond lengths are 2.20 Å. Both Zn(1)-O(4) bond lengths are 1.99 Å. In the second Zn site, Zn(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form ZnO6 octahedra that share corners with four equivalent V(1)O4 tetrahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with two equivalent Zn(2)O6 octahedra. The Zn(2)-O(2) bond length is 2.21 Å. The Zn(2)-O(3) bond length is 2.21 Å. Both Zn(2)-O(1) bond lengths are 2.20 Å. Both Zn(2)-O(4) bond lengths are 1.99 Å. H(1) is bonded in a single-bond geometry to one O(4) atom. The H(1)-O(4) bond length is 1.00 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Zn(2) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one Zn(1), and one Zn(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Zn(1), and one Zn(2) atom. In the fourth O site, O(4) is bonded to one Zn(1), two equivalent Zn(2), and one H(1) atom to form distorted corner-sharing OZn3H tetrahedra. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent V(1) atoms.