Sb2O5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form SbO6 octahedra that share corners with three equivalent Sb(2)O5 trigonal bipyramids,  an edgeedge with one Sb(1)O6 octahedra, and  an edgeedge with one Sb(2)O5 trigonal bipyramid. In the second Sb site, Sb(2) is bonded to one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form distorted SbO5 trigonal bipyramids that share corners with three equivalent Sb(1)O6 octahedra,  an edgeedge with one Sb(1)O6 octahedra, and  an edgeedge with one Sb(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-63°. There are five inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to two equivalent Sb(1) atoms. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Sb(1) and one Sb(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Sb(1) and one Sb(2) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Sb(1) and two equivalent Sb(2) atoms. In the fifth O site, O(5) is bonded in a water-like geometry to one Sb(1) and one Sb(2) atom.
Sb2O5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form SbO6 octahedra that share corners with three equivalent Sb(2)O5 trigonal bipyramids,  an edgeedge with one Sb(1)O6 octahedra, and  an edgeedge with one Sb(2)O5 trigonal bipyramid. The Sb(1)-O(2) bond length is 2.00 Å. The Sb(1)-O(3) bond length is 2.03 Å. The Sb(1)-O(4) bond length is 2.15 Å. The Sb(1)-O(5) bond length is 2.03 Å. Both Sb(1)-O(1) bond lengths are 1.99 Å. In the second Sb site, Sb(2) is bonded to one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form distorted SbO5 trigonal bipyramids that share corners with three equivalent Sb(1)O6 octahedra,  an edgeedge with one Sb(1)O6 octahedra, and  an edgeedge with one Sb(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-63°. The Sb(2)-O(2) bond length is 1.95 Å. The Sb(2)-O(3) bond length is 1.92 Å. The Sb(2)-O(5) bond length is 1.92 Å. There is one shorter (2.04 Å) and one longer (2.15 Å) Sb(2)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to two equivalent Sb(1) atoms. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Sb(1) and one Sb(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Sb(1) and one Sb(2) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Sb(1) and two equivalent Sb(2) atoms. In the fifth O site, O(5) is bonded in a water-like geometry to one Sb(1) and one Sb(2) atom.