Ga(Bi3O5)4 crystallizes in the cubic I23 space group. Ga(1) is bonded to four equivalent O(2) atoms to form GaO4 tetrahedra that share corners with twelve equivalent Bi(1)O5 square pyramids. Bi(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form distorted BiO5 square pyramids that share corners with eight equivalent Bi(1)O5 square pyramids,  a cornercorner with one Ga(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. There are three inequivalent O sites. In the first O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms. In the second O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the third O site, O(2) is bonded to one Ga(1) and three equivalent Bi(1) atoms to form distorted corner-sharing OGaBi3 tetrahedra.
Ga(Bi3O5)4 crystallizes in the cubic I23 space group. Ga(1) is bonded to four equivalent O(2) atoms to form GaO4 tetrahedra that share corners with twelve equivalent Bi(1)O5 square pyramids. All Ga(1)-O(2) bond lengths are 1.89 Å. Bi(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form distorted BiO5 square pyramids that share corners with eight equivalent Bi(1)O5 square pyramids,  a cornercorner with one Ga(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. The Bi(1)-O(2) bond length is 2.56 Å. The Bi(1)-O(3) bond length is 2.26 Å. There are a spread of Bi(1)-O(1) bond distances ranging from 2.11-2.59 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms. In the second O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the third O site, O(2) is bonded to one Ga(1) and three equivalent Bi(1) atoms to form distorted corner-sharing OGaBi3 tetrahedra.