La2Bi2S4OF crystallizes in the tetragonal P-4m2 space group. La(1) is bonded in a 4-coordinate geometry to one S(1), four equivalent S(2), two equivalent O(1), and two equivalent F(1) atoms. Bi(1) is bonded to one S(2) and five equivalent S(1) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one La(1) and five equivalent Bi(1) atoms to form SLaBi5 octahedra that share corners with four equivalent S(1)LaBi5 octahedra, corners with two equivalent O(1)La4 tetrahedra, corners with two equivalent F(1)La4 tetrahedra, and edges with eight equivalent S(1)LaBi5 octahedra. The corner-sharing octahedral tilt angles are 3°. In the second S site, S(2) is bonded in a 5-coordinate geometry to four equivalent La(1) and one Bi(1) atom. O(1) is bonded to four equivalent La(1) atoms to form OLa4 tetrahedra that share corners with four equivalent S(1)LaBi5 octahedra, corners with four equivalent O(1)La4 tetrahedra, and edges with four equivalent F(1)La4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. F(1) is bonded to four equivalent La(1) atoms to form FLa4 tetrahedra that share corners with four equivalent S(1)LaBi5 octahedra, corners with four equivalent F(1)La4 tetrahedra, and edges with four equivalent O(1)La4 tetrahedra. The corner-sharing octahedral tilt angles are 56°.
La2Bi2S4OF crystallizes in the tetragonal P-4m2 space group. La(1) is bonded in a 4-coordinate geometry to one S(1), four equivalent S(2), two equivalent O(1), and two equivalent F(1) atoms. The La(1)-S(1) bond length is 3.58 Å. All La(1)-S(2) bond lengths are 3.08 Å. Both La(1)-O(1) bond lengths are 2.48 Å. Both La(1)-F(1) bond lengths are 2.48 Å. Bi(1) is bonded to one S(2) and five equivalent S(1) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles are 3°. The Bi(1)-S(2) bond length is 2.63 Å. There are four shorter (2.91 Å) and one longer (3.13 Å) Bi(1)-S(1) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to one La(1) and five equivalent Bi(1) atoms to form SLaBi5 octahedra that share corners with four equivalent S(1)LaBi5 octahedra, corners with two equivalent O(1)La4 tetrahedra, corners with two equivalent F(1)La4 tetrahedra, and edges with eight equivalent S(1)LaBi5 octahedra. The corner-sharing octahedral tilt angles are 3°. In the second S site, S(2) is bonded in a 5-coordinate geometry to four equivalent La(1) and one Bi(1) atom. O(1) is bonded to four equivalent La(1) atoms to form OLa4 tetrahedra that share corners with four equivalent S(1)LaBi5 octahedra, corners with four equivalent O(1)La4 tetrahedra, and edges with four equivalent F(1)La4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. F(1) is bonded to four equivalent La(1) atoms to form FLa4 tetrahedra that share corners with four equivalent S(1)LaBi5 octahedra, corners with four equivalent F(1)La4 tetrahedra, and edges with four equivalent O(1)La4 tetrahedra. The corner-sharing octahedral tilt angles are 56°.