Na4SnSe4 crystallizes in the tetragonal P-42_1c space group. Na(1) is bonded to five equivalent Se(1) atoms to form distorted NaSe5 trigonal bipyramids that share corners with three equivalent Sn(1)Se4 tetrahedra, corners with ten equivalent Na(1)Se5 trigonal bipyramids,  an edgeedge with one Sn(1)Se4 tetrahedra, and edges with five equivalent Na(1)Se5 trigonal bipyramids. Sn(1) is bonded to four equivalent Se(1) atoms to form SnSe4 tetrahedra that share corners with twelve equivalent Na(1)Se5 trigonal bipyramids and edges with four equivalent Na(1)Se5 trigonal bipyramids. Se(1) is bonded in a 6-coordinate geometry to five equivalent Na(1) and one Sn(1) atom.
Na4SnSe4 crystallizes in the tetragonal P-42_1c space group. Na(1) is bonded to five equivalent Se(1) atoms to form distorted NaSe5 trigonal bipyramids that share corners with three equivalent Sn(1)Se4 tetrahedra, corners with ten equivalent Na(1)Se5 trigonal bipyramids,  an edgeedge with one Sn(1)Se4 tetrahedra, and edges with five equivalent Na(1)Se5 trigonal bipyramids. There are a spread of Na(1)-Se(1) bond distances ranging from 2.92-3.22 Å. Sn(1) is bonded to four equivalent Se(1) atoms to form SnSe4 tetrahedra that share corners with twelve equivalent Na(1)Se5 trigonal bipyramids and edges with four equivalent Na(1)Se5 trigonal bipyramids. All Sn(1)-Se(1) bond lengths are 2.54 Å. Se(1) is bonded in a 6-coordinate geometry to five equivalent Na(1) and one Sn(1) atom.