Na4SnS4 crystallizes in the tetragonal P-42_1c space group. Na(1) is bonded to five equivalent S(1) atoms to form distorted NaS5 trigonal bipyramids that share corners with three equivalent Sn(1)S4 tetrahedra, corners with ten equivalent Na(1)S5 trigonal bipyramids,  an edgeedge with one Sn(1)S4 tetrahedra, and edges with five equivalent Na(1)S5 trigonal bipyramids. Sn(1) is bonded to four equivalent S(1) atoms to form SnS4 tetrahedra that share corners with twelve equivalent Na(1)S5 trigonal bipyramids and edges with four equivalent Na(1)S5 trigonal bipyramids. S(1) is bonded in a 6-coordinate geometry to five equivalent Na(1) and one Sn(1) atom.
Na4SnS4 crystallizes in the tetragonal P-42_1c space group. Na(1) is bonded to five equivalent S(1) atoms to form distorted NaS5 trigonal bipyramids that share corners with three equivalent Sn(1)S4 tetrahedra, corners with ten equivalent Na(1)S5 trigonal bipyramids,  an edgeedge with one Sn(1)S4 tetrahedra, and edges with five equivalent Na(1)S5 trigonal bipyramids. There are a spread of Na(1)-S(1) bond distances ranging from 2.79-3.09 Å. Sn(1) is bonded to four equivalent S(1) atoms to form SnS4 tetrahedra that share corners with twelve equivalent Na(1)S5 trigonal bipyramids and edges with four equivalent Na(1)S5 trigonal bipyramids. All Sn(1)-S(1) bond lengths are 2.41 Å. S(1) is bonded in a 6-coordinate geometry to five equivalent Na(1) and one Sn(1) atom.