Materials Data on La4Bi4S8O3F by Materials Project

Abstract

La4Bi4S8O3F crystallizes in the tetragonal I-42m space group. The structure is three-dimensional. La3+ is bonded in a 4-coordinate geometry to four equivalent S2-, three O2-, and one F1- atom. There are two shorter (3.09 Å) and two longer (3.20 Å) La–S bond lengths. There are one shorter (2.36 Å) and two longer (2.44 Å) La–O bond lengths. The La–F bond length is 2.51 Å. Bi+2.75+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with four equivalent BiS6 octahedra, a cornercorner with one FLa4S4 tetrahedra, corners with three OLa4S4 tetrahedra, and edges with eight equivalent BiS6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are a spread of Bi–S bond distances ranging from 2.59–3.33 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded to five equivalent Bi+2.75+ atoms to form a mixture of edge and corner-sharing SBi5 square pyramids. In the second S2- site, S2- is bonded in a 1-coordinate geometry to four equivalent La3+, one Bi+2.75+, three O2-, and one F1- atom. There are two shorter (3.28 Å) and one longer (3.29 Å) S–O bond lengths. The S–F bond length is 3.28 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded to four equivalent La3+ and four equivalent S2- atoms to form OLa4S4 tetrahedra that share corners with four equivalent BiS6 octahedra, edges with four equivalent FLa4S4 tetrahedra, and faces with four equivalent OLa4S4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. In the second O2- site, O2- is bonded to four equivalent La3+ and four equivalent S2- atoms to form OLa4S4 tetrahedra that share corners with four equivalent BiS6 octahedra, edges with four equivalent OLa4S4 tetrahedra, faces with two equivalent OLa4S4 tetrahedra, and faces with two equivalent FLa4S4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. F1- is bonded to four equivalent La3+ and four equivalent S2- atoms to form distorted FLa4S4 tetrahedra that share corners with four equivalent BiS6 octahedra, edges with four equivalent OLa4S4 tetrahedra, and faces with four equivalent OLa4S4 tetrahedra. The corner-sharing octahedral tilt angles are 38°.