Nb3S5 crystallizes in the triclinic P1 space group. There are twelve inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one S(11), one S(13), one S(19), one S(20), one S(3), and one S(5) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 46°. In the second Nb site, Nb(2) is bonded to one S(15), one S(17), one S(4), one S(6), one S(7), and one S(9) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 44°. In the third Nb site, Nb(3) is bonded to one S(10), one S(15), one S(16), one S(17), one S(18), and one S(8) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 9-47°. In the fourth Nb site, Nb(4) is bonded to one S(1), one S(10), one S(11), one S(13), one S(2), and one S(8) atom to form a mixture of distorted face and edge-sharing NbS6 pentagonal pyramids. In the fifth Nb site, Nb(5) is bonded to one S(1), one S(12), one S(14), one S(19), one S(2), and one S(20) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 11-47°. In the sixth Nb site, Nb(6) is bonded to one S(12), one S(14), one S(15), one S(17), one S(3), and one S(5) atom to form a mixture of distorted face and edge-sharing NbS6 pentagonal pyramids. In the seventh Nb site, Nb(7) is bonded to one S(16), one S(18), one S(3), one S(4), one S(5), and one S(6) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. In the eighth Nb site, Nb(8) is bonded to one S(1), one S(16), one S(18), one S(2), one S(7), and one S(9) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. In the ninth Nb site, Nb(9) is bonded to one S(10), one S(19), one S(20), one S(7), one S(8), and one S(9) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 10-46°. In the tenth Nb site, Nb(10) is bonded to one S(11), one S(12), one S(13), one S(14), one S(4), and one S(6) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 9-46°. In the eleventh Nb site, Nb(11) is bonded to one S(1), one S(11), one S(18), one S(6), one S(8), and one S(9) atom to form a mixture of face, corner, and edge-sharing NbS6 octahedra. In the twelfth Nb site, Nb(12) is bonded to one S(10), one S(12), one S(13), one S(15), one S(20), and one S(3) atom to form a mixture of face, corner, and edge-sharing NbS6 octahedra. There are twenty inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(4), one Nb(5), and one Nb(8) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Nb(4), one Nb(5), and one Nb(8) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(12), one Nb(6), and one Nb(7) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Nb(10), one Nb(2), and one Nb(7) atom. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(6), and one Nb(7) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Nb(10), one Nb(11), one Nb(2), and one Nb(7) atom. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Nb(2), one Nb(8), and one Nb(9) atom. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(3), one Nb(4), and one Nb(9) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(2), one Nb(8), and one Nb(9) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Nb(12), one Nb(3), one Nb(4), and one Nb(9) atom. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(10), one Nb(11), and one Nb(4) atom. In the twelfth S site, S(12) is bonded to one Nb(10), one Nb(12), one Nb(5), and one Nb(6) atom to form edge-sharing SNb4 trigonal pyramids. In the thirteenth S site, S(13) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(10), one Nb(12), and one Nb(4) atom. In the fourteenth S site, S(14) is bonded in a distorted T-shaped geometry to one Nb(10), one Nb(5), and one Nb(6) atom. In the fifteenth S site, S(15) is bonded to one Nb(12), one Nb(2), one Nb(3), and one Nb(6) atom to form edge-sharing SNb4 trigonal pyramids. In the sixteenth S site, S(16) is bonded in a distorted T-shaped geometry to one Nb(3), one Nb(7), and one Nb(8) atom. In the seventeenth S site, S(17) is bonded in a distorted T-shaped geometry to one Nb(2), one Nb(3), and one Nb(6) atom. In the eighteenth S site, S(18) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(3), one Nb(7), and one Nb(8) atom. In the nineteenth S site, S(19) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(5), and one Nb(9) atom. In the twentieth S site, S(20) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(12), one Nb(5), and one Nb(9) atom.
Nb3S5 crystallizes in the triclinic P1 space group. There are twelve inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one S(11), one S(13), one S(19), one S(20), one S(3), and one S(5) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 46°. The Nb(1)-S(11) bond length is 2.53 Å. The Nb(1)-S(13) bond length is 2.54 Å. The Nb(1)-S(19) bond length is 2.49 Å. The Nb(1)-S(20) bond length is 2.49 Å. The Nb(1)-S(3) bond length is 2.53 Å. The Nb(1)-S(5) bond length is 2.49 Å. In the second Nb site, Nb(2) is bonded to one S(15), one S(17), one S(4), one S(6), one S(7), and one S(9) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 44°. The Nb(2)-S(15) bond length is 2.54 Å. The Nb(2)-S(17) bond length is 2.48 Å. The Nb(2)-S(4) bond length is 2.48 Å. The Nb(2)-S(6) bond length is 2.51 Å. The Nb(2)-S(7) bond length is 2.48 Å. The Nb(2)-S(9) bond length is 2.54 Å. In the third Nb site, Nb(3) is bonded to one S(10), one S(15), one S(16), one S(17), one S(18), and one S(8) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 9-47°. The Nb(3)-S(10) bond length is 2.47 Å. The Nb(3)-S(15) bond length is 2.50 Å. The Nb(3)-S(16) bond length is 2.49 Å. The Nb(3)-S(17) bond length is 2.49 Å. The Nb(3)-S(18) bond length is 2.42 Å. The Nb(3)-S(8) bond length is 2.54 Å. In the fourth Nb site, Nb(4) is bonded to one S(1), one S(10), one S(11), one S(13), one S(2), and one S(8) atom to form a mixture of distorted face and edge-sharing NbS6 pentagonal pyramids. The Nb(4)-S(1) bond length is 2.51 Å. The Nb(4)-S(10) bond length is 2.51 Å. The Nb(4)-S(11) bond length is 2.53 Å. The Nb(4)-S(13) bond length is 2.51 Å. The Nb(4)-S(2) bond length is 2.47 Å. The Nb(4)-S(8) bond length is 2.53 Å. In the fifth Nb site, Nb(5) is bonded to one S(1), one S(12), one S(14), one S(19), one S(2), and one S(20) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 11-47°. The Nb(5)-S(1) bond length is 2.50 Å. The Nb(5)-S(12) bond length is 2.51 Å. The Nb(5)-S(14) bond length is 2.47 Å. The Nb(5)-S(19) bond length is 2.50 Å. The Nb(5)-S(2) bond length is 2.50 Å. The Nb(5)-S(20) bond length is 2.44 Å. In the sixth Nb site, Nb(6) is bonded to one S(12), one S(14), one S(15), one S(17), one S(3), and one S(5) atom to form a mixture of distorted face and edge-sharing NbS6 pentagonal pyramids. The Nb(6)-S(12) bond length is 2.52 Å. The Nb(6)-S(14) bond length is 2.47 Å. The Nb(6)-S(15) bond length is 2.51 Å. The Nb(6)-S(17) bond length is 2.48 Å. The Nb(6)-S(3) bond length is 2.50 Å. The Nb(6)-S(5) bond length is 2.48 Å. In the seventh Nb site, Nb(7) is bonded to one S(16), one S(18), one S(3), one S(4), one S(5), and one S(6) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. The Nb(7)-S(16) bond length is 2.48 Å. The Nb(7)-S(18) bond length is 2.52 Å. The Nb(7)-S(3) bond length is 2.52 Å. The Nb(7)-S(4) bond length is 2.49 Å. The Nb(7)-S(5) bond length is 2.49 Å. The Nb(7)-S(6) bond length is 2.54 Å. In the eighth Nb site, Nb(8) is bonded to one S(1), one S(16), one S(18), one S(2), one S(7), and one S(9) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. The Nb(8)-S(1) bond length is 2.53 Å. The Nb(8)-S(16) bond length is 2.49 Å. The Nb(8)-S(18) bond length is 2.53 Å. The Nb(8)-S(2) bond length is 2.49 Å. The Nb(8)-S(7) bond length is 2.48 Å. The Nb(8)-S(9) bond length is 2.54 Å. In the ninth Nb site, Nb(9) is bonded to one S(10), one S(19), one S(20), one S(7), one S(8), and one S(9) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 10-46°. The Nb(9)-S(10) bond length is 2.52 Å. The Nb(9)-S(19) bond length is 2.47 Å. The Nb(9)-S(20) bond length is 2.52 Å. The Nb(9)-S(7) bond length is 2.52 Å. The Nb(9)-S(8) bond length is 2.52 Å. The Nb(9)-S(9) bond length is 2.46 Å. In the tenth Nb site, Nb(10) is bonded to one S(11), one S(12), one S(13), one S(14), one S(4), and one S(6) atom to form a mixture of distorted corner and edge-sharing NbS6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 9-46°. The Nb(10)-S(11) bond length is 2.54 Å. The Nb(10)-S(12) bond length is 2.49 Å. The Nb(10)-S(13) bond length is 2.46 Å. The Nb(10)-S(14) bond length is 2.47 Å. The Nb(10)-S(4) bond length is 2.49 Å. The Nb(10)-S(6) bond length is 2.45 Å. In the eleventh Nb site, Nb(11) is bonded to one S(1), one S(11), one S(18), one S(6), one S(8), and one S(9) atom to form a mixture of face, corner, and edge-sharing NbS6 octahedra. The Nb(11)-S(1) bond length is 2.57 Å. The Nb(11)-S(11) bond length is 2.56 Å. The Nb(11)-S(18) bond length is 2.38 Å. The Nb(11)-S(6) bond length is 2.39 Å. The Nb(11)-S(8) bond length is 2.55 Å. The Nb(11)-S(9) bond length is 2.40 Å. In the twelfth Nb site, Nb(12) is bonded to one S(10), one S(12), one S(13), one S(15), one S(20), and one S(3) atom to form a mixture of face, corner, and edge-sharing NbS6 octahedra. The Nb(12)-S(10) bond length is 2.40 Å. The Nb(12)-S(12) bond length is 2.56 Å. The Nb(12)-S(13) bond length is 2.38 Å. The Nb(12)-S(15) bond length is 2.55 Å. The Nb(12)-S(20) bond length is 2.39 Å. The Nb(12)-S(3) bond length is 2.59 Å. There are twenty inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(4), one Nb(5), and one Nb(8) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Nb(4), one Nb(5), and one Nb(8) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(12), one Nb(6), and one Nb(7) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Nb(10), one Nb(2), and one Nb(7) atom. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(6), and one Nb(7) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Nb(10), one Nb(11), one Nb(2), and one Nb(7) atom. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Nb(2), one Nb(8), and one Nb(9) atom. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(3), one Nb(4), and one Nb(9) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(2), one Nb(8), and one Nb(9) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Nb(12), one Nb(3), one Nb(4), and one Nb(9) atom. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(10), one Nb(11), and one Nb(4) atom. In the twelfth S site, S(12) is bonded to one Nb(10), one Nb(12), one Nb(5), and one Nb(6) atom to form edge-sharing SNb4 trigonal pyramids. In the thirteenth S site, S(13) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(10), one Nb(12), and one Nb(4) atom. In the fourteenth S site, S(14) is bonded in a distorted T-shaped geometry to one Nb(10), one Nb(5), and one Nb(6) atom. In the fifteenth S site, S(15) is bonded to one Nb(12), one Nb(2), one Nb(3), and one Nb(6) atom to form edge-sharing SNb4 trigonal pyramids. In the sixteenth S site, S(16) is bonded in a distorted T-shaped geometry to one Nb(3), one Nb(7), and one Nb(8) atom. In the seventeenth S site, S(17) is bonded in a distorted T-shaped geometry to one Nb(2), one Nb(3), and one Nb(6) atom. In the eighteenth S site, S(18) is bonded in a rectangular see-saw-like geometry to one Nb(11), one Nb(3), one Nb(7), and one Nb(8) atom. In the nineteenth S site, S(19) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(5), and one Nb(9) atom. In the twentieth S site, S(20) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Nb(12), one Nb(5), and one Nb(9) atom.