NaLa6Ga3S14 crystallizes in the trigonal P3 space group. Na(1) is bonded to three equivalent S(3) and three equivalent S(4) atoms to form distorted NaS6 octahedra that share faces with two equivalent Ga(3)S6 octahedra. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(1), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. In the second La site, La(2) is bonded in a 7-coordinate geometry to one S(2), one S(3), one S(6), two equivalent S(1), and two equivalent S(4) atoms. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a tetrahedral geometry to one S(6) and three equivalent S(1) atoms. In the second Ga site, Ga(2) is bonded in a tetrahedral geometry to one S(5) and three equivalent S(2) atoms. In the third Ga site, Ga(3) is bonded to three equivalent S(3) and three equivalent S(4) atoms to form distorted GaS6 octahedra that share faces with two equivalent Na(1)S6 octahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one La(1), two equivalent La(2), and one Ga(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one La(2), two equivalent La(1), and one Ga(2) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Na(1), one La(2), two equivalent La(1), and one Ga(3) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Na(1), two equivalent La(1), two equivalent La(2), and one Ga(3) atom. In the fifth S site, S(5) is bonded in a distorted tetrahedral geometry to three equivalent La(1) and one Ga(2) atom. In the sixth S site, S(6) is bonded in a tetrahedral geometry to three equivalent La(2) and one Ga(1) atom.
NaLa6Ga3S14 crystallizes in the trigonal P3 space group. Na(1) is bonded to three equivalent S(3) and three equivalent S(4) atoms to form distorted NaS6 octahedra that share faces with two equivalent Ga(3)S6 octahedra. All Na(1)-S(3) bond lengths are 2.75 Å. All Na(1)-S(4) bond lengths are 2.69 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(1), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. The La(1)-S(1) bond length is 3.07 Å. The La(1)-S(5) bond length is 2.95 Å. There is one shorter (2.84 Å) and one longer (2.95 Å) La(1)-S(2) bond length. There is one shorter (2.93 Å) and one longer (3.00 Å) La(1)-S(3) bond length. There is one shorter (3.28 Å) and one longer (3.32 Å) La(1)-S(4) bond length. In the second La site, La(2) is bonded in a 7-coordinate geometry to one S(2), one S(3), one S(6), two equivalent S(1), and two equivalent S(4) atoms. The La(2)-S(2) bond length is 3.06 Å. The La(2)-S(3) bond length is 2.98 Å. The La(2)-S(6) bond length is 2.93 Å. There is one shorter (2.91 Å) and one longer (3.00 Å) La(2)-S(1) bond length. Both La(2)-S(4) bond lengths are 2.94 Å. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a tetrahedral geometry to one S(6) and three equivalent S(1) atoms. The Ga(1)-S(6) bond length is 2.26 Å. All Ga(1)-S(1) bond lengths are 2.30 Å. In the second Ga site, Ga(2) is bonded in a tetrahedral geometry to one S(5) and three equivalent S(2) atoms. The Ga(2)-S(5) bond length is 2.26 Å. All Ga(2)-S(2) bond lengths are 2.30 Å. In the third Ga site, Ga(3) is bonded to three equivalent S(3) and three equivalent S(4) atoms to form distorted GaS6 octahedra that share faces with two equivalent Na(1)S6 octahedra. All Ga(3)-S(3) bond lengths are 2.48 Å. All Ga(3)-S(4) bond lengths are 2.62 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one La(1), two equivalent La(2), and one Ga(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one La(2), two equivalent La(1), and one Ga(2) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Na(1), one La(2), two equivalent La(1), and one Ga(3) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Na(1), two equivalent La(1), two equivalent La(2), and one Ga(3) atom. In the fifth S site, S(5) is bonded in a distorted tetrahedral geometry to three equivalent La(1) and one Ga(2) atom. In the sixth S site, S(6) is bonded in a tetrahedral geometry to three equivalent La(2) and one Ga(1) atom.