NaLi(AsS2)2 crystallizes in the triclinic P1 space group. Na(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form NaS6 octahedra that share corners with two equivalent Li(1)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, and edges with four equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. Li(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form LiS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Li(1)S6 octahedra, and edges with four equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. There are two inequivalent As sites. In the first As site, As(1) is bonded in a trigonal non-coplanar geometry to one S(2), one S(3), and one S(4) atom. In the second As site, As(2) is bonded in a trigonal non-coplanar geometry to one S(1), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), two equivalent Li(1), and one As(2) atom to form a mixture of corner and edge-sharing SNa2Li2As square pyramids. In the second S site, S(2) is bonded to two equivalent Na(1), two equivalent Li(1), and one As(1) atom to form a mixture of corner and edge-sharing SNa2Li2As square pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one Li(1), one As(1), and one As(2) atom. In the fourth S site, S(4) is bonded in a distorted see-saw-like geometry to one Na(1), one Li(1), one As(1), and one As(2) atom.
NaLi(AsS2)2 crystallizes in the triclinic P1 space group. Na(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form NaS6 octahedra that share corners with two equivalent Li(1)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, and edges with four equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. The Na(1)-S(3) bond length is 2.95 Å. The Na(1)-S(4) bond length is 3.07 Å. Both Na(1)-S(1) bond lengths are 2.85 Å. There is one shorter (2.78 Å) and one longer (2.79 Å) Na(1)-S(2) bond length. Li(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form LiS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Li(1)S6 octahedra, and edges with four equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. The Li(1)-S(3) bond length is 2.80 Å. The Li(1)-S(4) bond length is 2.73 Å. There is one shorter (2.72 Å) and one longer (2.84 Å) Li(1)-S(1) bond length. There is one shorter (2.81 Å) and one longer (2.89 Å) Li(1)-S(2) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded in a trigonal non-coplanar geometry to one S(2), one S(3), and one S(4) atom. The As(1)-S(2) bond length is 2.20 Å. The As(1)-S(3) bond length is 2.35 Å. The As(1)-S(4) bond length is 2.38 Å. In the second As site, As(2) is bonded in a trigonal non-coplanar geometry to one S(1), one S(3), and one S(4) atom. The As(2)-S(1) bond length is 2.20 Å. The As(2)-S(3) bond length is 2.37 Å. The As(2)-S(4) bond length is 2.36 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), two equivalent Li(1), and one As(2) atom to form a mixture of corner and edge-sharing SNa2Li2As square pyramids. In the second S site, S(2) is bonded to two equivalent Na(1), two equivalent Li(1), and one As(1) atom to form a mixture of corner and edge-sharing SNa2Li2As square pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one Li(1), one As(1), and one As(2) atom. In the fourth S site, S(4) is bonded in a distorted see-saw-like geometry to one Na(1), one Li(1), one As(1), and one As(2) atom.