NaAl(PS3)2 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form NaS6 octahedra that share corners with two equivalent Al(1)S6 octahedra, corners with six equivalent P(1)PS3 tetrahedra, and edges with two equivalent Al(1)S6 octahedra. The corner-sharing octahedral tilt angles are 11°. Al(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form AlS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with two equivalent P(1)PS3 tetrahedra, edges with two equivalent Na(1)S6 octahedra, and edges with two equivalent P(1)PS3 tetrahedra. The corner-sharing octahedral tilt angles are 11°. P(1) is bonded to one P(1), one S(1), one S(2), and one S(3) atom to form distorted PPS3 tetrahedra that share  a cornercorner with one Al(1)S6 octahedra, corners with three equivalent Na(1)S6 octahedra, and  an edgeedge with one Al(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 75-82°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Na(1), one Al(1), and one P(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one P(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one P(1) atom.
NaAl(PS3)2 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form NaS6 octahedra that share corners with two equivalent Al(1)S6 octahedra, corners with six equivalent P(1)PS3 tetrahedra, and edges with two equivalent Al(1)S6 octahedra. The corner-sharing octahedral tilt angles are 11°. Both Na(1)-S(1) bond lengths are 2.95 Å. Both Na(1)-S(2) bond lengths are 2.94 Å. Both Na(1)-S(3) bond lengths are 2.96 Å. Al(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form AlS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with two equivalent P(1)PS3 tetrahedra, edges with two equivalent Na(1)S6 octahedra, and edges with two equivalent P(1)PS3 tetrahedra. The corner-sharing octahedral tilt angles are 11°. Both Al(1)-S(1) bond lengths are 2.41 Å. Both Al(1)-S(2) bond lengths are 2.48 Å. Both Al(1)-S(3) bond lengths are 2.47 Å. P(1) is bonded to one P(1), one S(1), one S(2), and one S(3) atom to form distorted PPS3 tetrahedra that share  a cornercorner with one Al(1)S6 octahedra, corners with three equivalent Na(1)S6 octahedra, and  an edgeedge with one Al(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 75-82°. The P(1)-P(1) bond length is 2.25 Å. The P(1)-S(1) bond length is 2.06 Å. The P(1)-S(2) bond length is 2.03 Å. The P(1)-S(3) bond length is 2.03 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Na(1), one Al(1), and one P(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one P(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one P(1) atom.