Gd2V2O7 crystallizes in the cubic Fd-3m space group. Gd(1) is bonded to two equivalent O(2) and six equivalent O(1) atoms to form distorted GdO8 hexagonal bipyramids that share edges with six equivalent Gd(1)O8 hexagonal bipyramids and edges with six equivalent V(1)O6 octahedra. V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra and edges with six equivalent Gd(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Gd(1) and two equivalent V(1) atoms to form distorted OGd2V2 tetrahedra that share corners with two equivalent O(2)Gd4 tetrahedra, corners with twelve equivalent O(1)Gd2V2 tetrahedra,  an edgeedge with one O(2)Gd4 tetrahedra, and edges with four equivalent O(1)Gd2V2 tetrahedra. In the second O site, O(2) is bonded to four equivalent Gd(1) atoms to form OGd4 tetrahedra that share corners with four equivalent O(2)Gd4 tetrahedra, corners with twelve equivalent O(1)Gd2V2 tetrahedra, and edges with six equivalent O(1)Gd2V2 tetrahedra.
Gd2V2O7 crystallizes in the cubic Fd-3m space group. Gd(1) is bonded to two equivalent O(2) and six equivalent O(1) atoms to form distorted GdO8 hexagonal bipyramids that share edges with six equivalent Gd(1)O8 hexagonal bipyramids and edges with six equivalent V(1)O6 octahedra. Both Gd(1)-O(2) bond lengths are 2.21 Å. All Gd(1)-O(1) bond lengths are 2.50 Å. V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra and edges with six equivalent Gd(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. All V(1)-O(1) bond lengths are 1.97 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Gd(1) and two equivalent V(1) atoms to form distorted OGd2V2 tetrahedra that share corners with two equivalent O(2)Gd4 tetrahedra, corners with twelve equivalent O(1)Gd2V2 tetrahedra,  an edgeedge with one O(2)Gd4 tetrahedra, and edges with four equivalent O(1)Gd2V2 tetrahedra. In the second O site, O(2) is bonded to four equivalent Gd(1) atoms to form OGd4 tetrahedra that share corners with four equivalent O(2)Gd4 tetrahedra, corners with twelve equivalent O(1)Gd2V2 tetrahedra, and edges with six equivalent O(1)Gd2V2 tetrahedra.