La5S7 crystallizes in the monoclinic Cm space group. There are seven inequivalent La sites. In the first La site, La(1) is bonded in a distorted body-centered cubic geometry to two equivalent S(6), two equivalent S(7), and four equivalent S(2) atoms. In the second La site, La(2) is bonded in a distorted hexagonal planar geometry to two equivalent S(5) and four equivalent S(1) atoms. In the third La site, La(3) is bonded to one S(5), one S(6), one S(7), two equivalent S(3), and two equivalent S(4) atoms to form distorted LaS7 hexagonal pyramids that share edges with two equivalent La(3)S7 hexagonal pyramids and faces with two equivalent La(4)S6 pentagonal pyramids. In the fourth La site, La(4) is bonded to one S(1), one S(2), one S(3), one S(4), and two equivalent S(7) atoms to form distorted LaS6 pentagonal pyramids that share corners with two equivalent La(4)S6 pentagonal pyramids and faces with two equivalent La(3)S7 hexagonal pyramids. In the fifth La site, La(5) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(4), and four equivalent S(5) atoms. In the sixth La site, La(6) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), and four equivalent S(6) atoms. In the seventh La site, La(7) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. There are seven inequivalent S sites. In the first S site, S(1) is bonded to one La(4), one La(5), one La(7), and two equivalent La(2) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the second S site, S(2) is bonded to one La(4), one La(6), one La(7), and two equivalent La(1) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the third S site, S(3) is bonded to one La(4), one La(6), one La(7), and two equivalent La(3) atoms to form a mixture of edge, face, and corner-sharing SLa5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one La(4), one La(5), one La(7), and two equivalent La(3) atoms to form a mixture of edge, face, and corner-sharing SLa5 trigonal bipyramids. In the fifth S site, S(5) is bonded to one La(2), one La(3), one La(7), and two equivalent La(5) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the sixth S site, S(6) is bonded to one La(1), one La(3), one La(7), and two equivalent La(6) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one La(1), one La(3), and two equivalent La(4) atoms.
La5S7 crystallizes in the monoclinic Cm space group. There are seven inequivalent La sites. In the first La site, La(1) is bonded in a distorted body-centered cubic geometry to two equivalent S(6), two equivalent S(7), and four equivalent S(2) atoms. Both La(1)-S(6) bond lengths are 2.87 Å. Both La(1)-S(7) bond lengths are 3.18 Å. There are two shorter (3.10 Å) and two longer (3.12 Å) La(1)-S(2) bond lengths. In the second La site, La(2) is bonded in a distorted hexagonal planar geometry to two equivalent S(5) and four equivalent S(1) atoms. Both La(2)-S(5) bond lengths are 2.75 Å. There are two shorter (3.00 Å) and two longer (3.27 Å) La(2)-S(1) bond lengths. In the third La site, La(3) is bonded to one S(5), one S(6), one S(7), two equivalent S(3), and two equivalent S(4) atoms to form distorted LaS7 hexagonal pyramids that share edges with two equivalent La(3)S7 hexagonal pyramids and faces with two equivalent La(4)S6 pentagonal pyramids. The La(3)-S(5) bond length is 2.97 Å. The La(3)-S(6) bond length is 2.96 Å. The La(3)-S(7) bond length is 3.04 Å. There is one shorter (3.15 Å) and one longer (3.20 Å) La(3)-S(3) bond length. There is one shorter (3.07 Å) and one longer (3.16 Å) La(3)-S(4) bond length. In the fourth La site, La(4) is bonded to one S(1), one S(2), one S(3), one S(4), and two equivalent S(7) atoms to form distorted LaS6 pentagonal pyramids that share corners with two equivalent La(4)S6 pentagonal pyramids and faces with two equivalent La(3)S7 hexagonal pyramids. The La(4)-S(1) bond length is 2.82 Å. The La(4)-S(2) bond length is 2.86 Å. The La(4)-S(3) bond length is 2.80 Å. The La(4)-S(4) bond length is 2.83 Å. Both La(4)-S(7) bond lengths are 2.77 Å. In the fifth La site, La(5) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(4), and four equivalent S(5) atoms. Both La(5)-S(1) bond lengths are 3.08 Å. Both La(5)-S(4) bond lengths are 2.87 Å. There are two shorter (3.15 Å) and two longer (3.17 Å) La(5)-S(5) bond lengths. In the sixth La site, La(6) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), and four equivalent S(6) atoms. Both La(6)-S(2) bond lengths are 2.99 Å. Both La(6)-S(3) bond lengths are 2.93 Å. There are two shorter (3.11 Å) and two longer (3.17 Å) La(6)-S(6) bond lengths. In the seventh La site, La(7) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. The La(7)-S(1) bond length is 2.92 Å. The La(7)-S(2) bond length is 2.84 Å. The La(7)-S(3) bond length is 2.86 Å. The La(7)-S(4) bond length is 2.88 Å. The La(7)-S(5) bond length is 2.98 Å. The La(7)-S(6) bond length is 2.96 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded to one La(4), one La(5), one La(7), and two equivalent La(2) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the second S site, S(2) is bonded to one La(4), one La(6), one La(7), and two equivalent La(1) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the third S site, S(3) is bonded to one La(4), one La(6), one La(7), and two equivalent La(3) atoms to form a mixture of edge, face, and corner-sharing SLa5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one La(4), one La(5), one La(7), and two equivalent La(3) atoms to form a mixture of edge, face, and corner-sharing SLa5 trigonal bipyramids. In the fifth S site, S(5) is bonded to one La(2), one La(3), one La(7), and two equivalent La(5) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the sixth S site, S(6) is bonded to one La(1), one La(3), one La(7), and two equivalent La(6) atoms to form a mixture of distorted edge, face, and corner-sharing SLa5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one La(1), one La(3), and two equivalent La(4) atoms.