Bi2SeO6 crystallizes in the orthorhombic Cmce space group. Bi(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(3) atoms. Se(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing SeO6 octahedra. The corner-sharing octahedral tilt angles are 31°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Se(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Bi(1) and one Se(1) atom. In the third O site, O(3) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.
Bi2SeO6 crystallizes in the orthorhombic Cmce space group. Bi(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(3) atoms. The Bi(1)-O(2) bond length is 2.53 Å. There are two shorter (2.31 Å) and two longer (2.32 Å) Bi(1)-O(3) bond lengths. Se(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing SeO6 octahedra. The corner-sharing octahedral tilt angles are 31°. Both Se(1)-O(2) bond lengths are 1.75 Å. All Se(1)-O(1) bond lengths are 1.97 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Se(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Bi(1) and one Se(1) atom. In the third O site, O(3) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.