Cs4FeGa3S8 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(1), two equivalent S(5), and two equivalent S(7) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(2), two equivalent S(6), and two equivalent S(8) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one S(7), one S(8), two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to one S(7), one S(8), two equivalent S(2), two equivalent S(4), and two equivalent S(6) atoms. Fe(1) is bonded to one S(2), one S(3), one S(5), and one S(8) atom to form FeS4 tetrahedra that share edges with two equivalent Ga(3)S4 tetrahedra. There are two inequivalent Ga sites. In the first Ga site, Ga(1,2) is bonded to one S(1), one S(4), one S(6), and one S(7) atom to form edge-sharing GaS4 tetrahedra. In the second Ga site, Ga(3) is bonded to one S(2), one S(3), one S(5), and one S(8) atom to form GaS4 tetrahedra that share edges with two equivalent Fe(1)S4 tetrahedra. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1); two equivalent Cs(3); and two equivalent Ga(1,2) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Cs(2), two equivalent Cs(4), one Fe(1), and one Ga(3) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), two equivalent Cs(3), one Fe(1), and one Ga(3) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Cs(1); one Cs(2); two equivalent Cs(4); and two equivalent Ga(1,2) atoms. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(3), one Fe(1), and one Ga(3) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to two equivalent Cs(2); two equivalent Cs(4); and two equivalent Ga(1,2) atoms. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Cs(3); one Cs(4); two equivalent Cs(1); and two equivalent Ga(1,2) atoms. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Cs(3), one Cs(4), two equivalent Cs(2), one Fe(1), and one Ga(3) atom.
Cs4FeGa3S8 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(1), two equivalent S(5), and two equivalent S(7) atoms. The Cs(1)-S(3) bond length is 3.80 Å. The Cs(1)-S(4) bond length is 3.73 Å. There is one shorter (3.73 Å) and one longer (3.81 Å) Cs(1)-S(1) bond length. There is one shorter (3.75 Å) and one longer (3.76 Å) Cs(1)-S(5) bond length. Both Cs(1)-S(7) bond lengths are 3.76 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(2), two equivalent S(6), and two equivalent S(8) atoms. The Cs(2)-S(3) bond length is 3.73 Å. The Cs(2)-S(4) bond length is 3.81 Å. There is one shorter (3.73 Å) and one longer (3.80 Å) Cs(2)-S(2) bond length. Both Cs(2)-S(6) bond lengths are 3.76 Å. There is one shorter (3.75 Å) and one longer (3.76 Å) Cs(2)-S(8) bond length. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one S(7), one S(8), two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms. The Cs(3)-S(7) bond length is 3.81 Å. The Cs(3)-S(8) bond length is 3.73 Å. Both Cs(3)-S(1) bond lengths are 3.76 Å. There is one shorter (3.75 Å) and one longer (3.76 Å) Cs(3)-S(3) bond length. There is one shorter (3.74 Å) and one longer (3.80 Å) Cs(3)-S(5) bond length. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to one S(7), one S(8), two equivalent S(2), two equivalent S(4), and two equivalent S(6) atoms. The Cs(4)-S(7) bond length is 3.74 Å. The Cs(4)-S(8) bond length is 3.80 Å. There is one shorter (3.75 Å) and one longer (3.76 Å) Cs(4)-S(2) bond length. Both Cs(4)-S(4) bond lengths are 3.76 Å. There is one shorter (3.73 Å) and one longer (3.81 Å) Cs(4)-S(6) bond length. Fe(1) is bonded to one S(2), one S(3), one S(5), and one S(8) atom to form FeS4 tetrahedra that share edges with two equivalent Ga(3)S4 tetrahedra. The Fe(1)-S(2) bond length is 2.30 Å. The Fe(1)-S(3) bond length is 2.30 Å. The Fe(1)-S(5) bond length is 2.30 Å. The Fe(1)-S(8) bond length is 2.30 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(1,2) is bonded to one S(1), one S(4), one S(6), and one S(7) atom to form edge-sharing GaS4 tetrahedra. The Ga(1,2)-S(1) bond length is 2.30 Å. The Ga(1,2)-S(4) bond length is 2.30 Å. The Ga(1,2)-S(6) bond length is 2.31 Å. The Ga(1,2)-S(7) bond length is 2.31 Å. In the second Ga site, Ga(3) is bonded to one S(2), one S(3), one S(5), and one S(8) atom to form GaS4 tetrahedra that share edges with two equivalent Fe(1)S4 tetrahedra. The Ga(3)-S(2) bond length is 2.31 Å. The Ga(3)-S(3) bond length is 2.31 Å. The Ga(3)-S(5) bond length is 2.31 Å. The Ga(3)-S(8) bond length is 2.30 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1); two equivalent Cs(3); and two equivalent Ga(1,2) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Cs(2), two equivalent Cs(4), one Fe(1), and one Ga(3) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), two equivalent Cs(3), one Fe(1), and one Ga(3) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Cs(1); one Cs(2); two equivalent Cs(4); and two equivalent Ga(1,2) atoms. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(3), one Fe(1), and one Ga(3) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to two equivalent Cs(2); two equivalent Cs(4); and two equivalent Ga(1,2) atoms. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Cs(3); one Cs(4); two equivalent Cs(1); and two equivalent Ga(1,2) atoms. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Cs(3), one Cs(4), two equivalent Cs(2), one Fe(1), and one Ga(3) atom.