Cs3BiSe3 crystallizes in the cubic P2_13 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to six equivalent Se(1) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to six equivalent Se(1) atoms. In the third Cs site, Cs(3) is bonded in a 6-coordinate geometry to six equivalent Se(1) atoms. Bi(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Se(1) atoms. Se(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Bi(1) atom to form a mixture of distorted corner, edge, and face-sharing SeCs6Bi pentagonal bipyramids.
Cs3BiSe3 crystallizes in the cubic P2_13 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to six equivalent Se(1) atoms. There are three shorter (3.59 Å) and three longer (3.77 Å) Cs(1)-Se(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to six equivalent Se(1) atoms. There are three shorter (3.60 Å) and three longer (3.75 Å) Cs(2)-Se(1) bond lengths. In the third Cs site, Cs(3) is bonded in a 6-coordinate geometry to six equivalent Se(1) atoms. There are three shorter (3.87 Å) and three longer (3.98 Å) Cs(3)-Se(1) bond lengths. Bi(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Se(1) atoms. All Bi(1)-Se(1) bond lengths are 2.68 Å. Se(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Bi(1) atom to form a mixture of distorted corner, edge, and face-sharing SeCs6Bi pentagonal bipyramids.