K2La2Sb2S9 crystallizes in the orthorhombic Pbam space group. K(1) is bonded to one S(3), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of distorted face and corner-sharing KS7 pentagonal bipyramids. La(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. Sb(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), two equivalent S(3), and two equivalent S(5) atoms. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(1), two equivalent La(1), and one Sb(1) atom to form SK2La2Sb square pyramids that share edges with two equivalent S(3)K2Sb4 octahedra and edges with two equivalent S(1)K2La2Sb square pyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent K(1), two equivalent La(1), one Sb(1), and one S(4) atom. In the third S site, S(3) is bonded to two equivalent K(1) and four equivalent Sb(1) atoms to form SK2Sb4 octahedra that share edges with two equivalent S(3)K2Sb4 octahedra and edges with four equivalent S(1)K2La2Sb square pyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent La(1), and one S(2) atom. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to two equivalent La(1) and two equivalent Sb(1) atoms.
K2La2Sb2S9 crystallizes in the orthorhombic Pbam space group. K(1) is bonded to one S(3), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of distorted face and corner-sharing KS7 pentagonal bipyramids. The K(1)-S(3) bond length is 3.34 Å. Both K(1)-S(1) bond lengths are 3.22 Å. Both K(1)-S(2) bond lengths are 3.28 Å. Both K(1)-S(4) bond lengths are 3.33 Å. La(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. Both La(1)-S(1) bond lengths are 2.96 Å. Both La(1)-S(2) bond lengths are 2.94 Å. Both La(1)-S(4) bond lengths are 2.89 Å. There is one shorter (2.97 Å) and one longer (3.05 Å) La(1)-S(5) bond length. Sb(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), two equivalent S(3), and two equivalent S(5) atoms. The Sb(1)-S(1) bond length is 2.48 Å. The Sb(1)-S(2) bond length is 3.17 Å. Both Sb(1)-S(3) bond lengths are 2.93 Å. Both Sb(1)-S(5) bond lengths are 2.73 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(1), two equivalent La(1), and one Sb(1) atom to form SK2La2Sb square pyramids that share edges with two equivalent S(3)K2Sb4 octahedra and edges with two equivalent S(1)K2La2Sb square pyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent K(1), two equivalent La(1), one Sb(1), and one S(4) atom. The S(2)-S(4) bond length is 2.11 Å. In the third S site, S(3) is bonded to two equivalent K(1) and four equivalent Sb(1) atoms to form SK2Sb4 octahedra that share edges with two equivalent S(3)K2Sb4 octahedra and edges with four equivalent S(1)K2La2Sb square pyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent La(1), and one S(2) atom. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to two equivalent La(1) and two equivalent Sb(1) atoms.