KCd4Ga5S12 crystallizes in the triclinic P1 space group. K(1) is bonded in a 8-coordinate geometry to one S(10), one S(11), one S(12), one S(3), one S(4), one S(5), one S(6), and one S(9) atom. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one S(3), one S(4), one S(8), and one S(9) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the second Cd site, Cd(2) is bonded to one S(1), one S(10), one S(2), and one S(4) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the third Cd site, Cd(3) is bonded to one S(11), one S(2), one S(3), and one S(5) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the fourth Cd site, Cd(4) is bonded to one S(1), one S(12), one S(3), and one S(6) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. There are five inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one S(11), one S(12), one S(4), and one S(7) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the second Ga site, Ga(2) is bonded to one S(10), one S(12), one S(5), and one S(8) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the third Ga site, Ga(3) is bonded to one S(10), one S(11), one S(6), and one S(9) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the fourth Ga site, Ga(4) is bonded to one S(1), one S(5), one S(7), and one S(9) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. In the fifth Ga site, Ga(5) is bonded to one S(2), one S(6), one S(7), and one S(8) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra, and  a cornercorner with one Ga(4)S4 tetrahedra. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Cd(2), one Cd(4), and one Ga(4) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cd(2), one Cd(3), and one Ga(5) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one K(1), one Cd(1), one Cd(3), and one Cd(4) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one K(1), one Cd(1), one Cd(2), and one Ga(1) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(3), one Ga(2), and one Ga(4) atom. In the sixth S site, S(6) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(4), one Ga(3), and one Ga(5) atom. In the seventh S site, S(7) is bonded in a trigonal non-coplanar geometry to one Ga(1), one Ga(4), and one Ga(5) atom. In the eighth S site, S(8) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Ga(2), and one Ga(5) atom. In the ninth S site, S(9) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(1), one Ga(3), and one Ga(4) atom. In the tenth S site, S(10) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(2), one Ga(2), and one Ga(3) atom. In the eleventh S site, S(11) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(3), one Ga(1), and one Ga(3) atom. In the twelfth S site, S(12) is bonded in a trigonal non-coplanar geometry to one K(1), one Cd(4), one Ga(1), and one Ga(2) atom.
KCd4Ga5S12 crystallizes in the triclinic P1 space group. K(1) is bonded in a 8-coordinate geometry to one S(10), one S(11), one S(12), one S(3), one S(4), one S(5), one S(6), and one S(9) atom. The K(1)-S(10) bond length is 3.73 Å. The K(1)-S(11) bond length is 3.72 Å. The K(1)-S(12) bond length is 3.80 Å. The K(1)-S(3) bond length is 3.42 Å. The K(1)-S(4) bond length is 3.53 Å. The K(1)-S(5) bond length is 3.70 Å. The K(1)-S(6) bond length is 3.73 Å. The K(1)-S(9) bond length is 3.72 Å. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one S(3), one S(4), one S(8), and one S(9) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Cd(1)-S(3) bond length is 2.50 Å. The Cd(1)-S(4) bond length is 2.54 Å. The Cd(1)-S(8) bond length is 2.61 Å. The Cd(1)-S(9) bond length is 2.63 Å. In the second Cd site, Cd(2) is bonded to one S(1), one S(10), one S(2), and one S(4) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Cd(2)-S(1) bond length is 2.54 Å. The Cd(2)-S(10) bond length is 2.59 Å. The Cd(2)-S(2) bond length is 2.56 Å. The Cd(2)-S(4) bond length is 2.54 Å. In the third Cd site, Cd(3) is bonded to one S(11), one S(2), one S(3), and one S(5) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Cd(3)-S(11) bond length is 2.62 Å. The Cd(3)-S(2) bond length is 2.54 Å. The Cd(3)-S(3) bond length is 2.51 Å. The Cd(3)-S(5) bond length is 2.57 Å. In the fourth Cd site, Cd(4) is bonded to one S(1), one S(12), one S(3), and one S(6) atom to form CdS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Cd(4)-S(1) bond length is 2.55 Å. The Cd(4)-S(12) bond length is 2.60 Å. The Cd(4)-S(3) bond length is 2.49 Å. The Cd(4)-S(6) bond length is 2.58 Å. There are five inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one S(11), one S(12), one S(4), and one S(7) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Ga(1)-S(11) bond length is 2.31 Å. The Ga(1)-S(12) bond length is 2.34 Å. The Ga(1)-S(4) bond length is 2.25 Å. The Ga(1)-S(7) bond length is 2.39 Å. In the second Ga site, Ga(2) is bonded to one S(10), one S(12), one S(5), and one S(8) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Ga(2)-S(10) bond length is 2.32 Å. The Ga(2)-S(12) bond length is 2.32 Å. The Ga(2)-S(5) bond length is 2.29 Å. The Ga(2)-S(8) bond length is 2.32 Å. In the third Ga site, Ga(3) is bonded to one S(10), one S(11), one S(6), and one S(9) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(4)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Ga(3)-S(10) bond length is 2.30 Å. The Ga(3)-S(11) bond length is 2.33 Å. The Ga(3)-S(6) bond length is 2.30 Å. The Ga(3)-S(9) bond length is 2.33 Å. In the fourth Ga site, Ga(4) is bonded to one S(1), one S(5), one S(7), and one S(9) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra, and  a cornercorner with one Ga(5)S4 tetrahedra. The Ga(4)-S(1) bond length is 2.25 Å. The Ga(4)-S(5) bond length is 2.32 Å. The Ga(4)-S(7) bond length is 2.39 Å. The Ga(4)-S(9) bond length is 2.32 Å. In the fifth Ga site, Ga(5) is bonded to one S(2), one S(6), one S(7), and one S(8) atom to form GaS4 tetrahedra that share  a cornercorner with one Cd(1)S4 tetrahedra,  a cornercorner with one Cd(2)S4 tetrahedra,  a cornercorner with one Cd(3)S4 tetrahedra,  a cornercorner with one Cd(4)S4 tetrahedra,  a cornercorner with one Ga(1)S4 tetrahedra,  a cornercorner with one Ga(2)S4 tetrahedra,  a cornercorner with one Ga(3)S4 tetrahedra, and  a cornercorner with one Ga(4)S4 tetrahedra. The Ga(5)-S(2) bond length is 2.26 Å. The Ga(5)-S(6) bond length is 2.32 Å. The Ga(5)-S(7) bond length is 2.36 Å. The Ga(5)-S(8) bond length is 2.33 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Cd(2), one Cd(4), and one Ga(4) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cd(2), one Cd(3), and one Ga(5) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one K(1), one Cd(1), one Cd(3), and one Cd(4) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one K(1), one Cd(1), one Cd(2), and one Ga(1) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(3), one Ga(2), and one Ga(4) atom. In the sixth S site, S(6) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(4), one Ga(3), and one Ga(5) atom. In the seventh S site, S(7) is bonded in a trigonal non-coplanar geometry to one Ga(1), one Ga(4), and one Ga(5) atom. In the eighth S site, S(8) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Ga(2), and one Ga(5) atom. In the ninth S site, S(9) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(1), one Ga(3), and one Ga(4) atom. In the tenth S site, S(10) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(2), one Ga(2), and one Ga(3) atom. In the eleventh S site, S(11) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Cd(3), one Ga(1), and one Ga(3) atom. In the twelfth S site, S(12) is bonded in a trigonal non-coplanar geometry to one K(1), one Cd(4), one Ga(1), and one Ga(2) atom.