Ba6Nb5S17 crystallizes in the triclinic P1 space group. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to one S(1), one S(11), one S(16), one S(17), one S(2), one S(3), one S(4), one S(5), one S(7), one S(8), and one S(9) atom. In the second Ba site, Ba(2) is bonded to one S(1), one S(12), one S(14), one S(15), one S(16), one S(17), one S(3), one S(4), one S(5), one S(6), one S(7), and one S(8) atom to form BaS12 cuboctahedra that share  a cornercorner with one Nb(1)S6 octahedra,  a cornercorner with one Nb(3)S6 octahedra,  a cornercorner with one Nb(5)S6 octahedra,  a cornercorner with one Nb(2)S5 square pyramid, faces with two equivalent Ba(5)S12 cuboctahedra,  a faceface with one Nb(1)S6 octahedra,  a faceface with one Nb(3)S6 octahedra,  a faceface with one Nb(5)S6 octahedra, and  a faceface with one Nb(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 18-22°. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one S(10), one S(12), one S(13), one S(14), one S(15), one S(16), one S(5), one S(6), one S(7), one S(8), and one S(9) atom. In the fourth Ba site, Ba(4) is bonded in a 11-coordinate geometry to one S(10), one S(11), one S(12), one S(13), one S(2), one S(3), one S(4), one S(5), one S(6), one S(8), and one S(9) atom. In the fifth Ba site, Ba(5) is bonded to one S(1), one S(10), one S(11), one S(12), one S(13), one S(14), one S(15), one S(17), one S(2), one S(3), one S(4), and one S(6) atom to form distorted BaS12 cuboctahedra that share  a cornercorner with one Nb(1)S6 octahedra,  a cornercorner with one Nb(3)S6 octahedra,  a cornercorner with one Nb(5)S6 octahedra,  a cornercorner with one Nb(2)S5 square pyramid, faces with two equivalent Ba(2)S12 cuboctahedra,  a faceface with one Nb(1)S6 octahedra,  a faceface with one Nb(3)S6 octahedra,  a faceface with one Nb(5)S6 octahedra, and  a faceface with one Nb(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 22-28°. In the sixth Ba site, Ba(6) is bonded in a 11-coordinate geometry to one S(1), one S(10), one S(11), one S(13), one S(14), one S(15), one S(16), one S(17), one S(2), one S(7), and one S(9) atom. There are five inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one S(10), one S(14), one S(16), one S(2), one S(4), and one S(8) atom to form NbS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra,  a faceface with one Nb(5)S6 octahedra, and  a faceface with one Nb(2)S5 square pyramid. In the second Nb site, Nb(2) is bonded to one S(1), one S(14), one S(2), one S(6), and one S(8) atom to form distorted NbS5 square pyramids that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra, and  a faceface with one Nb(1)S6 octahedra. In the third Nb site, Nb(3) is bonded to one S(11), one S(12), one S(15), one S(17), one S(5), and one S(9) atom to form NbS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra, and  a faceface with one Nb(5)S6 octahedra. In the fourth Nb site, Nb(4) is bonded in a 6-coordinate geometry to one S(11), one S(13), one S(15), one S(3), one S(5), and one S(7) atom. In the fifth Nb site, Nb(5) is bonded to one S(10), one S(12), one S(16), one S(17), one S(4), and one S(9) atom to form NbS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra,  a faceface with one Nb(1)S6 octahedra, and  a faceface with one Nb(3)S6 octahedra. There are seventeen inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(5), one Ba(6), and one Nb(2) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(4), one Ba(5), one Ba(6), one Nb(1), and one Nb(2) atom. In the third S site, S(3) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(4), one Ba(5), and one Nb(4) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), one Ba(5), one Nb(1), and one Nb(5) atom. In the fifth S site, S(5) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Nb(3), and one Nb(4) atom to form a mixture of distorted corner, edge, and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 8-58°. In the sixth S site, S(6) is bonded in a 1-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(5), and one Nb(2) atom. In the seventh S site, S(7) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(6), and one Nb(4) atom. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Nb(1), and one Nb(2) atom. In the ninth S site, S(9) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(3), one Ba(4), one Ba(6), one Nb(3), and one Nb(5) atom. In the tenth S site, S(10) is bonded in a 6-coordinate geometry to one Ba(3), one Ba(4), one Ba(5), one Ba(6), one Nb(1), and one Nb(5) atom. In the eleventh S site, S(11) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(4), one Ba(5), one Ba(6), one Nb(3), and one Nb(4) atom. In the twelfth S site, S(12) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(5), one Nb(3), and one Nb(5) atom. In the thirteenth S site, S(13) is bonded in a distorted single-bond geometry to one Ba(3), one Ba(4), one Ba(5), one Ba(6), and one Nb(4) atom. In the fourteenth S site, S(14) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ba(5), one Ba(6), one Nb(1), and one Nb(2) atom. In the fifteenth S site, S(15) is bonded to one Ba(2), one Ba(3), one Ba(5), one Ba(6), one Nb(3), and one Nb(4) atom to form a mixture of distorted corner and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 35-59°. In the sixteenth S site, S(16) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(6), one Nb(1), and one Nb(5) atom to form a mixture of distorted corner and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 33-58°. In the seventeenth S site, S(17) is bonded to one Ba(1), one Ba(2), one Ba(5), one Ba(6), one Nb(3), and one Nb(5) atom to form a mixture of distorted corner, edge, and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 8-59°.
Ba6Nb5S17 crystallizes in the triclinic P1 space group. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to one S(1), one S(11), one S(16), one S(17), one S(2), one S(3), one S(4), one S(5), one S(7), one S(8), and one S(9) atom. The Ba(1)-S(1) bond length is 3.57 Å. The Ba(1)-S(11) bond length is 3.34 Å. The Ba(1)-S(16) bond length is 3.34 Å. The Ba(1)-S(17) bond length is 3.31 Å. The Ba(1)-S(2) bond length is 3.34 Å. The Ba(1)-S(3) bond length is 3.47 Å. The Ba(1)-S(4) bond length is 3.58 Å. The Ba(1)-S(5) bond length is 3.29 Å. The Ba(1)-S(7) bond length is 3.51 Å. The Ba(1)-S(8) bond length is 3.73 Å. The Ba(1)-S(9) bond length is 3.40 Å. In the second Ba site, Ba(2) is bonded to one S(1), one S(12), one S(14), one S(15), one S(16), one S(17), one S(3), one S(4), one S(5), one S(6), one S(7), and one S(8) atom to form BaS12 cuboctahedra that share  a cornercorner with one Nb(1)S6 octahedra,  a cornercorner with one Nb(3)S6 octahedra,  a cornercorner with one Nb(5)S6 octahedra,  a cornercorner with one Nb(2)S5 square pyramid, faces with two equivalent Ba(5)S12 cuboctahedra,  a faceface with one Nb(1)S6 octahedra,  a faceface with one Nb(3)S6 octahedra,  a faceface with one Nb(5)S6 octahedra, and  a faceface with one Nb(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 18-22°. The Ba(2)-S(1) bond length is 3.51 Å. The Ba(2)-S(12) bond length is 3.52 Å. The Ba(2)-S(14) bond length is 3.46 Å. The Ba(2)-S(15) bond length is 3.40 Å. The Ba(2)-S(16) bond length is 3.50 Å. The Ba(2)-S(17) bond length is 3.39 Å. The Ba(2)-S(3) bond length is 3.50 Å. The Ba(2)-S(4) bond length is 3.62 Å. The Ba(2)-S(5) bond length is 3.45 Å. The Ba(2)-S(6) bond length is 3.46 Å. The Ba(2)-S(7) bond length is 3.46 Å. The Ba(2)-S(8) bond length is 3.61 Å. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one S(10), one S(12), one S(13), one S(14), one S(15), one S(16), one S(5), one S(6), one S(7), one S(8), and one S(9) atom. The Ba(3)-S(10) bond length is 3.47 Å. The Ba(3)-S(12) bond length is 3.53 Å. The Ba(3)-S(13) bond length is 3.80 Å. The Ba(3)-S(14) bond length is 3.37 Å. The Ba(3)-S(15) bond length is 3.33 Å. The Ba(3)-S(16) bond length is 3.52 Å. The Ba(3)-S(5) bond length is 3.31 Å. The Ba(3)-S(6) bond length is 3.28 Å. The Ba(3)-S(7) bond length is 3.35 Å. The Ba(3)-S(8) bond length is 3.40 Å. The Ba(3)-S(9) bond length is 3.46 Å. In the fourth Ba site, Ba(4) is bonded in a 11-coordinate geometry to one S(10), one S(11), one S(12), one S(13), one S(2), one S(3), one S(4), one S(5), one S(6), one S(8), and one S(9) atom. The Ba(4)-S(10) bond length is 3.66 Å. The Ba(4)-S(11) bond length is 3.49 Å. The Ba(4)-S(12) bond length is 3.37 Å. The Ba(4)-S(13) bond length is 3.30 Å. The Ba(4)-S(2) bond length is 3.46 Å. The Ba(4)-S(3) bond length is 3.33 Å. The Ba(4)-S(4) bond length is 3.32 Å. The Ba(4)-S(5) bond length is 3.57 Å. The Ba(4)-S(6) bond length is 3.35 Å. The Ba(4)-S(8) bond length is 3.46 Å. The Ba(4)-S(9) bond length is 3.54 Å. In the fifth Ba site, Ba(5) is bonded to one S(1), one S(10), one S(11), one S(12), one S(13), one S(14), one S(15), one S(17), one S(2), one S(3), one S(4), and one S(6) atom to form distorted BaS12 cuboctahedra that share  a cornercorner with one Nb(1)S6 octahedra,  a cornercorner with one Nb(3)S6 octahedra,  a cornercorner with one Nb(5)S6 octahedra,  a cornercorner with one Nb(2)S5 square pyramid, faces with two equivalent Ba(2)S12 cuboctahedra,  a faceface with one Nb(1)S6 octahedra,  a faceface with one Nb(3)S6 octahedra,  a faceface with one Nb(5)S6 octahedra, and  a faceface with one Nb(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 22-28°. The Ba(5)-S(1) bond length is 3.42 Å. The Ba(5)-S(10) bond length is 3.52 Å. The Ba(5)-S(11) bond length is 3.49 Å. The Ba(5)-S(12) bond length is 3.54 Å. The Ba(5)-S(13) bond length is 3.30 Å. The Ba(5)-S(14) bond length is 3.72 Å. The Ba(5)-S(15) bond length is 3.43 Å. The Ba(5)-S(17) bond length is 3.46 Å. The Ba(5)-S(2) bond length is 3.70 Å. The Ba(5)-S(3) bond length is 3.34 Å. The Ba(5)-S(4) bond length is 3.39 Å. The Ba(5)-S(6) bond length is 3.75 Å. In the sixth Ba site, Ba(6) is bonded in a 11-coordinate geometry to one S(1), one S(10), one S(11), one S(13), one S(14), one S(15), one S(16), one S(17), one S(2), one S(7), and one S(9) atom. The Ba(6)-S(1) bond length is 3.28 Å. The Ba(6)-S(10) bond length is 3.51 Å. The Ba(6)-S(11) bond length is 3.47 Å. The Ba(6)-S(13) bond length is 3.36 Å. The Ba(6)-S(14) bond length is 3.55 Å. The Ba(6)-S(15) bond length is 3.53 Å. The Ba(6)-S(16) bond length is 3.38 Å. The Ba(6)-S(17) bond length is 3.48 Å. The Ba(6)-S(2) bond length is 3.48 Å. The Ba(6)-S(7) bond length is 3.44 Å. The Ba(6)-S(9) bond length is 3.68 Å. There are five inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one S(10), one S(14), one S(16), one S(2), one S(4), and one S(8) atom to form NbS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra,  a faceface with one Nb(5)S6 octahedra, and  a faceface with one Nb(2)S5 square pyramid. The Nb(1)-S(10) bond length is 2.52 Å. The Nb(1)-S(14) bond length is 2.55 Å. The Nb(1)-S(16) bond length is 2.49 Å. The Nb(1)-S(2) bond length is 2.50 Å. The Nb(1)-S(4) bond length is 2.44 Å. The Nb(1)-S(8) bond length is 2.47 Å. In the second Nb site, Nb(2) is bonded to one S(1), one S(14), one S(2), one S(6), and one S(8) atom to form distorted NbS5 square pyramids that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra, and  a faceface with one Nb(1)S6 octahedra. The Nb(2)-S(1) bond length is 2.31 Å. The Nb(2)-S(14) bond length is 2.31 Å. The Nb(2)-S(2) bond length is 2.55 Å. The Nb(2)-S(6) bond length is 2.31 Å. The Nb(2)-S(8) bond length is 2.57 Å. In the third Nb site, Nb(3) is bonded to one S(11), one S(12), one S(15), one S(17), one S(5), and one S(9) atom to form NbS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra, and  a faceface with one Nb(5)S6 octahedra. The Nb(3)-S(11) bond length is 2.39 Å. The Nb(3)-S(12) bond length is 2.63 Å. The Nb(3)-S(15) bond length is 2.46 Å. The Nb(3)-S(17) bond length is 2.47 Å. The Nb(3)-S(5) bond length is 2.52 Å. The Nb(3)-S(9) bond length is 2.49 Å. In the fourth Nb site, Nb(4) is bonded in a 6-coordinate geometry to one S(11), one S(13), one S(15), one S(3), one S(5), and one S(7) atom. The Nb(4)-S(11) bond length is 3.07 Å. The Nb(4)-S(13) bond length is 2.34 Å. The Nb(4)-S(15) bond length is 2.64 Å. The Nb(4)-S(3) bond length is 2.30 Å. The Nb(4)-S(5) bond length is 2.59 Å. The Nb(4)-S(7) bond length is 2.28 Å. In the fifth Nb site, Nb(5) is bonded to one S(10), one S(12), one S(16), one S(17), one S(4), and one S(9) atom to form NbS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(5)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(5)S12 cuboctahedra,  a faceface with one Nb(1)S6 octahedra, and  a faceface with one Nb(3)S6 octahedra. The Nb(5)-S(10) bond length is 2.52 Å. The Nb(5)-S(12) bond length is 2.43 Å. The Nb(5)-S(16) bond length is 2.54 Å. The Nb(5)-S(17) bond length is 2.53 Å. The Nb(5)-S(4) bond length is 2.53 Å. The Nb(5)-S(9) bond length is 2.45 Å. There are seventeen inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(5), one Ba(6), and one Nb(2) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(4), one Ba(5), one Ba(6), one Nb(1), and one Nb(2) atom. In the third S site, S(3) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(4), one Ba(5), and one Nb(4) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), one Ba(5), one Nb(1), and one Nb(5) atom. In the fifth S site, S(5) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Nb(3), and one Nb(4) atom to form a mixture of distorted corner, edge, and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 8-58°. In the sixth S site, S(6) is bonded in a 1-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(5), and one Nb(2) atom. In the seventh S site, S(7) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(6), and one Nb(4) atom. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Nb(1), and one Nb(2) atom. In the ninth S site, S(9) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(3), one Ba(4), one Ba(6), one Nb(3), and one Nb(5) atom. In the tenth S site, S(10) is bonded in a 6-coordinate geometry to one Ba(3), one Ba(4), one Ba(5), one Ba(6), one Nb(1), and one Nb(5) atom. In the eleventh S site, S(11) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(4), one Ba(5), one Ba(6), one Nb(3), and one Nb(4) atom. In the twelfth S site, S(12) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(5), one Nb(3), and one Nb(5) atom. In the thirteenth S site, S(13) is bonded in a distorted single-bond geometry to one Ba(3), one Ba(4), one Ba(5), one Ba(6), and one Nb(4) atom. In the fourteenth S site, S(14) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ba(5), one Ba(6), one Nb(1), and one Nb(2) atom. In the fifteenth S site, S(15) is bonded to one Ba(2), one Ba(3), one Ba(5), one Ba(6), one Nb(3), and one Nb(4) atom to form a mixture of distorted corner and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 35-59°. In the sixteenth S site, S(16) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(6), one Nb(1), and one Nb(5) atom to form a mixture of distorted corner and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 33-58°. In the seventeenth S site, S(17) is bonded to one Ba(1), one Ba(2), one Ba(5), one Ba(6), one Nb(3), and one Nb(5) atom to form a mixture of distorted corner, edge, and face-sharing SBa4Nb2 octahedra. The corner-sharing octahedral tilt angles range from 8-59°.