Na5InS4 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted NaS4 tetrahedra that share corners with four equivalent Na(4)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent Na(1)S4 tetrahedra, corners with two equivalent Na(3)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra,  an edgeedge with one Na(4)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid,  an edgeedge with one Na(1)S4 tetrahedra,  an edgeedge with one Na(3)S4 tetrahedra, and  an edgeedge with one In(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-57°. In the second Na site, Na(2) is bonded to one S(3) and four equivalent S(2) atoms to form distorted NaS5 square pyramids that share corners with two equivalent Na(4)S6 octahedra, corners with three equivalent Na(3)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, corners with six equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Na(2)S5 square pyramids,  an edgeedge with one Na(3)S4 tetrahedra,  an edgeedge with one In(1)S4 tetrahedra, and edges with two equivalent Na(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 82°. In the third Na site, Na(3) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted NaS4 tetrahedra that share corners with two equivalent Na(4)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent In(1)S4 tetrahedra, corners with four equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid,  an edgeedge with one In(1)S4 tetrahedra, and edges with two equivalent Na(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the fourth Na site, Na(4) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted NaS6 octahedra that share corners with two equivalent Na(2)S5 square pyramids, corners with two equivalent Na(3)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra, corners with eight equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Na(2)S5 square pyramids, edges with two equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(3)S4 tetrahedra, and edges with two equivalent In(1)S4 tetrahedra. In(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form InS4 tetrahedra that share corners with two equivalent Na(4)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent Na(3)S4 tetrahedra, corners with four equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid,  an edgeedge with one Na(3)S4 tetrahedra, and edges with two equivalent Na(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Na(3), two equivalent Na(1), two equivalent Na(4), and one In(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Na(3), one Na(4), two equivalent Na(1), two equivalent Na(2), and one In(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), two equivalent Na(4), and one In(1) atom.
Na5InS4 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted NaS4 tetrahedra that share corners with four equivalent Na(4)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent Na(1)S4 tetrahedra, corners with two equivalent Na(3)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra,  an edgeedge with one Na(4)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid,  an edgeedge with one Na(1)S4 tetrahedra,  an edgeedge with one Na(3)S4 tetrahedra, and  an edgeedge with one In(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-57°. The Na(1)-S(1) bond length is 2.70 Å. The Na(1)-S(3) bond length is 2.70 Å. There is one shorter (2.75 Å) and one longer (2.88 Å) Na(1)-S(2) bond length. In the second Na site, Na(2) is bonded to one S(3) and four equivalent S(2) atoms to form distorted NaS5 square pyramids that share corners with two equivalent Na(4)S6 octahedra, corners with three equivalent Na(3)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, corners with six equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Na(2)S5 square pyramids,  an edgeedge with one Na(3)S4 tetrahedra,  an edgeedge with one In(1)S4 tetrahedra, and edges with two equivalent Na(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 82°. The Na(2)-S(3) bond length is 2.85 Å. There are two shorter (2.89 Å) and two longer (3.14 Å) Na(2)-S(2) bond lengths. In the third Na site, Na(3) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted NaS4 tetrahedra that share corners with two equivalent Na(4)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent In(1)S4 tetrahedra, corners with four equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid,  an edgeedge with one In(1)S4 tetrahedra, and edges with two equivalent Na(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The Na(3)-S(1) bond length is 2.91 Å. The Na(3)-S(3) bond length is 2.69 Å. Both Na(3)-S(2) bond lengths are 2.76 Å. In the fourth Na site, Na(4) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted NaS6 octahedra that share corners with two equivalent Na(2)S5 square pyramids, corners with two equivalent Na(3)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra, corners with eight equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Na(2)S5 square pyramids, edges with two equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(3)S4 tetrahedra, and edges with two equivalent In(1)S4 tetrahedra. Both Na(4)-S(1) bond lengths are 2.87 Å. Both Na(4)-S(2) bond lengths are 3.04 Å. Both Na(4)-S(3) bond lengths are 3.16 Å. In(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form InS4 tetrahedra that share corners with two equivalent Na(4)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent Na(3)S4 tetrahedra, corners with four equivalent Na(1)S4 tetrahedra, edges with two equivalent Na(4)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid,  an edgeedge with one Na(3)S4 tetrahedra, and edges with two equivalent Na(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The In(1)-S(1) bond length is 2.47 Å. The In(1)-S(3) bond length is 2.49 Å. Both In(1)-S(2) bond lengths are 2.50 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Na(3), two equivalent Na(1), two equivalent Na(4), and one In(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Na(3), one Na(4), two equivalent Na(1), two equivalent Na(2), and one In(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), two equivalent Na(4), and one In(1) atom.