Pb4SBr6 crystallizes in the triclinic P1 space group. There are four inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one S(1), two equivalent Br(1), and two equivalent Br(2) atoms to form edge-sharing PbSBr4 square pyramids. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one Br(5), two equivalent Br(2), two equivalent Br(4), and two equivalent Br(6) atoms. In the third Pb site, Pb(3) is bonded in a see-saw-like geometry to two equivalent S(1), one Br(5), and one Br(6) atom. In the fourth Pb site, Pb(4) is bonded in a 7-coordinate geometry to one Br(6), two equivalent Br(1), two equivalent Br(3), and two equivalent Br(5) atoms. S(1) is bonded in a trigonal planar geometry to one Pb(1) and two equivalent Pb(3) atoms. There are six inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted L-shaped geometry to two equivalent Pb(1) and two equivalent Pb(4) atoms. In the second Br site, Br(2) is bonded in a 4-coordinate geometry to two equivalent Pb(1) and two equivalent Pb(2) atoms. In the third Br site, Br(3) is bonded in an L-shaped geometry to two equivalent Pb(4) atoms. In the fourth Br site, Br(4) is bonded in an L-shaped geometry to two equivalent Pb(2) atoms. In the fifth Br site, Br(5) is bonded to one Pb(2), one Pb(3), and two equivalent Pb(4) atoms to form corner-sharing BrPb4 tetrahedra. In the sixth Br site, Br(6) is bonded to one Pb(3), one Pb(4), and two equivalent Pb(2) atoms to form corner-sharing BrPb4 tetrahedra.
Pb4SBr6 crystallizes in the triclinic P1 space group. There are four inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one S(1), two equivalent Br(1), and two equivalent Br(2) atoms to form edge-sharing PbSBr4 square pyramids. The Pb(1)-S(1) bond length is 2.69 Å. Both Pb(1)-Br(1) bond lengths are 3.10 Å. Both Pb(1)-Br(2) bond lengths are 3.10 Å. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one Br(5), two equivalent Br(2), two equivalent Br(4), and two equivalent Br(6) atoms. The Pb(2)-Br(5) bond length is 3.22 Å. There is one shorter (3.36 Å) and one longer (3.41 Å) Pb(2)-Br(2) bond length. There is one shorter (3.01 Å) and one longer (3.05 Å) Pb(2)-Br(4) bond length. There is one shorter (3.12 Å) and one longer (3.14 Å) Pb(2)-Br(6) bond length. In the third Pb site, Pb(3) is bonded in a see-saw-like geometry to two equivalent S(1), one Br(5), and one Br(6) atom. Both Pb(3)-S(1) bond lengths are 2.73 Å. The Pb(3)-Br(5) bond length is 3.10 Å. The Pb(3)-Br(6) bond length is 3.10 Å. In the fourth Pb site, Pb(4) is bonded in a 7-coordinate geometry to one Br(6), two equivalent Br(1), two equivalent Br(3), and two equivalent Br(5) atoms. The Pb(4)-Br(6) bond length is 3.22 Å. Both Pb(4)-Br(1) bond lengths are 3.39 Å. There is one shorter (3.02 Å) and one longer (3.03 Å) Pb(4)-Br(3) bond length. Both Pb(4)-Br(5) bond lengths are 3.13 Å. S(1) is bonded in a trigonal planar geometry to one Pb(1) and two equivalent Pb(3) atoms. There are six inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted L-shaped geometry to two equivalent Pb(1) and two equivalent Pb(4) atoms. In the second Br site, Br(2) is bonded in a 4-coordinate geometry to two equivalent Pb(1) and two equivalent Pb(2) atoms. In the third Br site, Br(3) is bonded in an L-shaped geometry to two equivalent Pb(4) atoms. In the fourth Br site, Br(4) is bonded in an L-shaped geometry to two equivalent Pb(2) atoms. In the fifth Br site, Br(5) is bonded to one Pb(2), one Pb(3), and two equivalent Pb(4) atoms to form corner-sharing BrPb4 tetrahedra. In the sixth Br site, Br(6) is bonded to one Pb(3), one Pb(4), and two equivalent Pb(2) atoms to form corner-sharing BrPb4 tetrahedra.