Gd2V2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(5), two equivalent O(4), and two equivalent O(7) atoms. In the second Gd site, Gd(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form distorted GdO7 pentagonal bipyramids that share corners with four equivalent V(2)O4 tetrahedra, corners with three equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Gd(2)O7 pentagonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(5) atoms to form distorted VO5 trigonal bipyramids that share corners with three equivalent Gd(2)O7 pentagonal bipyramids,  a cornercorner with one V(2)O4 tetrahedra,  an edgeedge with one Gd(2)O7 pentagonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. In the second V site, V(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form VO4 tetrahedra that share corners with four equivalent Gd(2)O7 pentagonal bipyramids and  a cornercorner with one V(1)O5 trigonal bipyramid. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Gd(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Gd(1), one Gd(2), and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Gd(1), one Gd(2), and one V(1) atom. In the fourth O site, O(4) is bonded to one Gd(2), two equivalent Gd(1), and one V(2) atom to form distorted edge-sharing OGd3V tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Gd(2) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Gd(1) and one V(2) atom.
Gd2V2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(5), two equivalent O(4), and two equivalent O(7) atoms. The Gd(1)-O(2) bond length is 2.22 Å. The Gd(1)-O(3) bond length is 2.39 Å. The Gd(1)-O(5) bond length is 2.81 Å. There is one shorter (2.43 Å) and one longer (2.58 Å) Gd(1)-O(4) bond length. There is one shorter (2.34 Å) and one longer (2.37 Å) Gd(1)-O(7) bond length. In the second Gd site, Gd(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form distorted GdO7 pentagonal bipyramids that share corners with four equivalent V(2)O4 tetrahedra, corners with three equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Gd(2)O7 pentagonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Gd(2)-O(1) bond length is 2.44 Å. The Gd(2)-O(2) bond length is 2.27 Å. The Gd(2)-O(3) bond length is 2.44 Å. The Gd(2)-O(4) bond length is 2.43 Å. The Gd(2)-O(5) bond length is 2.39 Å. There is one shorter (2.37 Å) and one longer (2.40 Å) Gd(2)-O(6) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(5) atoms to form distorted VO5 trigonal bipyramids that share corners with three equivalent Gd(2)O7 pentagonal bipyramids,  a cornercorner with one V(2)O4 tetrahedra,  an edgeedge with one Gd(2)O7 pentagonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 1.86 Å. The V(1)-O(3) bond length is 1.74 Å. There is one shorter (1.91 Å) and one longer (1.98 Å) V(1)-O(5) bond length. In the second V site, V(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form VO4 tetrahedra that share corners with four equivalent Gd(2)O7 pentagonal bipyramids and  a cornercorner with one V(1)O5 trigonal bipyramid. The V(2)-O(1) bond length is 1.80 Å. The V(2)-O(4) bond length is 1.86 Å. The V(2)-O(6) bond length is 1.81 Å. The V(2)-O(7) bond length is 1.81 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Gd(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Gd(1), one Gd(2), and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Gd(1), one Gd(2), and one V(1) atom. In the fourth O site, O(4) is bonded to one Gd(2), two equivalent Gd(1), and one V(2) atom to form distorted edge-sharing OGd3V tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Gd(2) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Gd(1) and one V(2) atom.