NaNbS6 crystallizes in the monoclinic Cc space group. Na(1) is bonded in a 9-coordinate geometry to one S(1), one S(3), one S(6), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. Nb(1) is bonded in a 9-coordinate geometry to one S(2), one S(4), one S(5), two equivalent S(1), two equivalent S(3), and two equivalent S(6) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(1), and one S(4) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Nb(1), and one S(3) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(1), and one S(2) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Nb(1), and one S(1) atom. In the fifth S site, S(5) is bonded to two equivalent Na(1), one Nb(1), and one S(6) atom to form distorted corner-sharing SNa2NbS tetrahedra. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(1), and one S(5) atom.
NaNbS6 crystallizes in the monoclinic Cc space group. Na(1) is bonded in a 9-coordinate geometry to one S(1), one S(3), one S(6), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. The Na(1)-S(1) bond length is 3.03 Å. The Na(1)-S(3) bond length is 3.08 Å. The Na(1)-S(6) bond length is 3.20 Å. There is one shorter (2.96 Å) and one longer (3.26 Å) Na(1)-S(2) bond length. There is one shorter (3.11 Å) and one longer (3.42 Å) Na(1)-S(4) bond length. There is one shorter (2.92 Å) and one longer (3.14 Å) Na(1)-S(5) bond length. Nb(1) is bonded in a 9-coordinate geometry to one S(2), one S(4), one S(5), two equivalent S(1), two equivalent S(3), and two equivalent S(6) atoms. The Nb(1)-S(2) bond length is 2.56 Å. The Nb(1)-S(4) bond length is 2.54 Å. The Nb(1)-S(5) bond length is 2.51 Å. There is one shorter (2.53 Å) and one longer (2.75 Å) Nb(1)-S(1) bond length. There is one shorter (2.53 Å) and one longer (2.60 Å) Nb(1)-S(3) bond length. There is one shorter (2.62 Å) and one longer (2.66 Å) Nb(1)-S(6) bond length. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(1), and one S(4) atom. The S(1)-S(4) bond length is 2.05 Å. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Nb(1), and one S(3) atom. The S(2)-S(3) bond length is 2.04 Å. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(1), and one S(2) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Nb(1), and one S(1) atom. In the fifth S site, S(5) is bonded to two equivalent Na(1), one Nb(1), and one S(6) atom to form distorted corner-sharing SNa2NbS tetrahedra. The S(5)-S(6) bond length is 2.05 Å. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(1), and one S(5) atom.