Mg(NbS3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one S(11), one S(12), one S(5), one S(7), one S(8), and one S(9) atom. There are four inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 8-coordinate geometry to one S(12), one S(2), one S(3), one S(5), one S(8), one S(9), and two equivalent S(6) atoms. In the second Nb site, Nb(2) is bonded in a 8-coordinate geometry to one S(12), one S(2), one S(3), one S(5), one S(8), one S(9), and two equivalent S(4) atoms. In the third Nb site, Nb(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(11), one S(4), one S(6), one S(7), and two equivalent S(2) atoms. In the fourth Nb site, Nb(4) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(11), one S(4), one S(6), one S(7), and two equivalent S(3) atoms. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Nb(3), one Nb(4), and one S(10) atom. In the second S site, S(2) is bonded to one Nb(1), one Nb(2), and two equivalent Nb(3) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the third S site, S(3) is bonded to one Nb(1), one Nb(2), and two equivalent Nb(4) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the fourth S site, S(4) is bonded to one Nb(3), one Nb(4), and two equivalent Nb(2) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom. In the sixth S site, S(6) is bonded to one Nb(3), one Nb(4), and two equivalent Nb(1) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(3), and one Nb(4) atom. In the eighth S site, S(8) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom. In the ninth S site, S(9) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Nb(3), one Nb(4), and one S(1) atom. In the eleventh S site, S(11) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(3), and one Nb(4) atom. In the twelfth S site, S(12) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom.
Mg(NbS3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one S(11), one S(12), one S(5), one S(7), one S(8), and one S(9) atom. The Mg(1)-S(11) bond length is 2.49 Å. The Mg(1)-S(12) bond length is 2.66 Å. The Mg(1)-S(5) bond length is 2.72 Å. The Mg(1)-S(7) bond length is 2.58 Å. The Mg(1)-S(8) bond length is 2.55 Å. The Mg(1)-S(9) bond length is 2.60 Å. There are four inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 8-coordinate geometry to one S(12), one S(2), one S(3), one S(5), one S(8), one S(9), and two equivalent S(6) atoms. The Nb(1)-S(12) bond length is 2.59 Å. The Nb(1)-S(2) bond length is 2.61 Å. The Nb(1)-S(3) bond length is 2.51 Å. The Nb(1)-S(5) bond length is 2.52 Å. The Nb(1)-S(8) bond length is 2.59 Å. The Nb(1)-S(9) bond length is 2.54 Å. There is one shorter (2.70 Å) and one longer (2.72 Å) Nb(1)-S(6) bond length. In the second Nb site, Nb(2) is bonded in a 8-coordinate geometry to one S(12), one S(2), one S(3), one S(5), one S(8), one S(9), and two equivalent S(4) atoms. The Nb(2)-S(12) bond length is 2.60 Å. The Nb(2)-S(2) bond length is 2.59 Å. The Nb(2)-S(3) bond length is 2.48 Å. The Nb(2)-S(5) bond length is 2.53 Å. The Nb(2)-S(8) bond length is 2.60 Å. The Nb(2)-S(9) bond length is 2.53 Å. There is one shorter (2.68 Å) and one longer (2.70 Å) Nb(2)-S(4) bond length. In the third Nb site, Nb(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(11), one S(4), one S(6), one S(7), and two equivalent S(2) atoms. The Nb(3)-S(1) bond length is 2.51 Å. The Nb(3)-S(10) bond length is 2.56 Å. The Nb(3)-S(11) bond length is 2.63 Å. The Nb(3)-S(4) bond length is 2.50 Å. The Nb(3)-S(6) bond length is 2.57 Å. The Nb(3)-S(7) bond length is 2.62 Å. There is one shorter (2.69 Å) and one longer (2.71 Å) Nb(3)-S(2) bond length. In the fourth Nb site, Nb(4) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(11), one S(4), one S(6), one S(7), and two equivalent S(3) atoms. The Nb(4)-S(1) bond length is 2.50 Å. The Nb(4)-S(10) bond length is 2.55 Å. The Nb(4)-S(11) bond length is 2.61 Å. The Nb(4)-S(4) bond length is 2.47 Å. The Nb(4)-S(6) bond length is 2.56 Å. The Nb(4)-S(7) bond length is 2.61 Å. There is one shorter (2.67 Å) and one longer (2.68 Å) Nb(4)-S(3) bond length. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Nb(3), one Nb(4), and one S(10) atom. The S(1)-S(10) bond length is 2.02 Å. In the second S site, S(2) is bonded to one Nb(1), one Nb(2), and two equivalent Nb(3) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the third S site, S(3) is bonded to one Nb(1), one Nb(2), and two equivalent Nb(4) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the fourth S site, S(4) is bonded to one Nb(3), one Nb(4), and two equivalent Nb(2) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom. In the sixth S site, S(6) is bonded to one Nb(3), one Nb(4), and two equivalent Nb(1) atoms to form a mixture of distorted corner and edge-sharing SNb4 tetrahedra. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(3), and one Nb(4) atom. In the eighth S site, S(8) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom. In the ninth S site, S(9) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Nb(3), one Nb(4), and one S(1) atom. In the eleventh S site, S(11) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(3), and one Nb(4) atom. In the twelfth S site, S(12) is bonded in a 3-coordinate geometry to one Mg(1), one Nb(1), and one Nb(2) atom.