Ba4In2Te2Se5 crystallizes in the tetragonal P4/mbm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent Se(2) and six equivalent Se(1) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to four equivalent Te(1), one Se(2), and four equivalent Se(1) atoms. In(1) is bonded to two equivalent Te(1) and two equivalent Se(1) atoms to form distorted edge-sharing InTe2Se2 tetrahedra. Te(1) is bonded in a 6-coordinate geometry to four equivalent Ba(2) and two equivalent In(1) atoms. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Ba(2), three equivalent Ba(1), and one In(1) atom to form distorted SeBa5In pentagonal pyramids that share corners with two equivalent Se(2)Ba6 octahedra, corners with six equivalent Se(1)Ba5In pentagonal pyramids, edges with five equivalent Se(1)Ba5In pentagonal pyramids, faces with two equivalent Se(2)Ba6 octahedra, and faces with two equivalent Se(1)Ba5In pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. In the second Se site, Se(2) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form SeBa6 octahedra that share corners with four equivalent Se(2)Ba6 octahedra, corners with eight equivalent Se(1)Ba5In pentagonal pyramids, and faces with eight equivalent Se(1)Ba5In pentagonal pyramids. The corner-sharing octahedral tilt angles are 41°.
Ba4In2Te2Se5 crystallizes in the tetragonal P4/mbm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent Se(2) and six equivalent Se(1) atoms. Both Ba(1)-Se(2) bond lengths are 3.30 Å. There are two shorter (3.22 Å) and four longer (3.59 Å) Ba(1)-Se(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to four equivalent Te(1), one Se(2), and four equivalent Se(1) atoms. All Ba(2)-Te(1) bond lengths are 4.06 Å. The Ba(2)-Se(2) bond length is 3.27 Å. All Ba(2)-Se(1) bond lengths are 3.45 Å. In(1) is bonded to two equivalent Te(1) and two equivalent Se(1) atoms to form distorted edge-sharing InTe2Se2 tetrahedra. Both In(1)-Te(1) bond lengths are 2.85 Å. Both In(1)-Se(1) bond lengths are 2.59 Å. Te(1) is bonded in a 6-coordinate geometry to four equivalent Ba(2) and two equivalent In(1) atoms. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Ba(2), three equivalent Ba(1), and one In(1) atom to form distorted SeBa5In pentagonal pyramids that share corners with two equivalent Se(2)Ba6 octahedra, corners with six equivalent Se(1)Ba5In pentagonal pyramids, edges with five equivalent Se(1)Ba5In pentagonal pyramids, faces with two equivalent Se(2)Ba6 octahedra, and faces with two equivalent Se(1)Ba5In pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. In the second Se site, Se(2) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form SeBa6 octahedra that share corners with four equivalent Se(2)Ba6 octahedra, corners with eight equivalent Se(1)Ba5In pentagonal pyramids, and faces with eight equivalent Se(1)Ba5In pentagonal pyramids. The corner-sharing octahedral tilt angles are 41°.