BiYO3 crystallizes in the hexagonal P6_3cm space group. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in a 7-coordinate geometry to one O(1), three equivalent O(3), and three equivalent O(4) atoms. In the second Y site, Y(2) is bonded in a 7-coordinate geometry to one O(2), three equivalent O(3), and three equivalent O(4) atoms. Bi(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form corner-sharing BiO5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Y(1) and three equivalent Bi(1) atoms to form OYBi3 tetrahedra that share corners with three equivalent O(1)YBi3 tetrahedra, corners with three equivalent O(2)YBi3 tetrahedra, corners with six equivalent O(3)Y3Bi tetrahedra, and edges with three equivalent O(4)Y3Bi tetrahedra. In the second O site, O(2) is bonded to one Y(2) and three equivalent Bi(1) atoms to form OYBi3 tetrahedra that share corners with six equivalent O(4)Y3Bi tetrahedra, corners with six equivalent O(1)YBi3 tetrahedra, and edges with three equivalent O(3)Y3Bi tetrahedra. In the third O site, O(3) is bonded to one Y(2), two equivalent Y(1), and one Bi(1) atom to form distorted OY3Bi tetrahedra that share corners with four equivalent O(4)Y3Bi tetrahedra, corners with four equivalent O(1)YBi3 tetrahedra, corners with six equivalent O(3)Y3Bi tetrahedra,  an edgeedge with one O(2)YBi3 tetrahedra, and edges with three equivalent O(4)Y3Bi tetrahedra. In the fourth O site, O(4) is bonded to one Y(2), two equivalent Y(1), and one Bi(1) atom to form OY3Bi tetrahedra that share corners with two equivalent O(2)YBi3 tetrahedra, corners with four equivalent O(3)Y3Bi tetrahedra, corners with six equivalent O(4)Y3Bi tetrahedra, edges with two equivalent O(1)YBi3 tetrahedra, and edges with three equivalent O(3)Y3Bi tetrahedra.
BiYO3 crystallizes in the hexagonal P6_3cm space group. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in a 7-coordinate geometry to one O(1), three equivalent O(3), and three equivalent O(4) atoms. The Y(1)-O(1) bond length is 2.54 Å. All Y(1)-O(3) bond lengths are 2.37 Å. All Y(1)-O(4) bond lengths are 2.44 Å. In the second Y site, Y(2) is bonded in a 7-coordinate geometry to one O(2), three equivalent O(3), and three equivalent O(4) atoms. The Y(2)-O(2) bond length is 2.46 Å. All Y(2)-O(3) bond lengths are 2.60 Å. All Y(2)-O(4) bond lengths are 2.28 Å. Bi(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form corner-sharing BiO5 trigonal bipyramids. The Bi(1)-O(2) bond length is 2.29 Å. The Bi(1)-O(3) bond length is 2.33 Å. The Bi(1)-O(4) bond length is 2.34 Å. Both Bi(1)-O(1) bond lengths are 2.27 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Y(1) and three equivalent Bi(1) atoms to form OYBi3 tetrahedra that share corners with three equivalent O(1)YBi3 tetrahedra, corners with three equivalent O(2)YBi3 tetrahedra, corners with six equivalent O(3)Y3Bi tetrahedra, and edges with three equivalent O(4)Y3Bi tetrahedra. In the second O site, O(2) is bonded to one Y(2) and three equivalent Bi(1) atoms to form OYBi3 tetrahedra that share corners with six equivalent O(4)Y3Bi tetrahedra, corners with six equivalent O(1)YBi3 tetrahedra, and edges with three equivalent O(3)Y3Bi tetrahedra. In the third O site, O(3) is bonded to one Y(2), two equivalent Y(1), and one Bi(1) atom to form distorted OY3Bi tetrahedra that share corners with four equivalent O(4)Y3Bi tetrahedra, corners with four equivalent O(1)YBi3 tetrahedra, corners with six equivalent O(3)Y3Bi tetrahedra,  an edgeedge with one O(2)YBi3 tetrahedra, and edges with three equivalent O(4)Y3Bi tetrahedra. In the fourth O site, O(4) is bonded to one Y(2), two equivalent Y(1), and one Bi(1) atom to form OY3Bi tetrahedra that share corners with two equivalent O(2)YBi3 tetrahedra, corners with four equivalent O(3)Y3Bi tetrahedra, corners with six equivalent O(4)Y3Bi tetrahedra, edges with two equivalent O(1)YBi3 tetrahedra, and edges with three equivalent O(3)Y3Bi tetrahedra.