NaSCN crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to three equivalent N(1) and three equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing NaS3N3 octahedra. The corner-sharing octahedral tilt angles are 57°. C(1) is bonded in a distorted linear geometry to one N(1) and one S(1) atom. N(1) is bonded to three equivalent Na(1) and one C(1) atom to form distorted NNa3C tetrahedra that share corners with two equivalent N(1)Na3C tetrahedra, corners with eight equivalent S(1)Na3C tetrahedra,  an edgeedge with one S(1)Na3C tetrahedra, and edges with two equivalent N(1)Na3C tetrahedra. S(1) is bonded to three equivalent Na(1) and one C(1) atom to form SNa3C tetrahedra that share corners with six equivalent S(1)Na3C tetrahedra, corners with eight equivalent N(1)Na3C tetrahedra, and  an edgeedge with one N(1)Na3C tetrahedra.
NaSCN crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to three equivalent N(1) and three equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing NaS3N3 octahedra. The corner-sharing octahedral tilt angles are 57°. There is one shorter (2.45 Å) and two longer (2.59 Å) Na(1)-N(1) bond lengths. There are two shorter (2.98 Å) and one longer (3.04 Å) Na(1)-S(1) bond length. C(1) is bonded in a distorted linear geometry to one N(1) and one S(1) atom. The C(1)-N(1) bond length is 1.19 Å. The C(1)-S(1) bond length is 1.63 Å. N(1) is bonded to three equivalent Na(1) and one C(1) atom to form distorted NNa3C tetrahedra that share corners with two equivalent N(1)Na3C tetrahedra, corners with eight equivalent S(1)Na3C tetrahedra,  an edgeedge with one S(1)Na3C tetrahedra, and edges with two equivalent N(1)Na3C tetrahedra. S(1) is bonded to three equivalent Na(1) and one C(1) atom to form SNa3C tetrahedra that share corners with six equivalent S(1)Na3C tetrahedra, corners with eight equivalent N(1)Na3C tetrahedra, and  an edgeedge with one N(1)Na3C tetrahedra.