Y4N2S3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Y sites. In the first Y site, Y(1) is bonded in a 2-coordinate geometry to two equivalent N(1) and four equivalent S(2) atoms. In the second Y site, Y(2) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent S(1), and two equivalent S(2) atoms. In the third Y site, Y(3) is bonded in a 6-coordinate geometry to two equivalent N(1), one S(1), and three equivalent S(2) atoms. N(1) is bonded to one Y(1), one Y(2), and two equivalent Y(3) atoms to form NY4 tetrahedra that share corners with six equivalent S(2)Y6 octahedra, edges with three equivalent S(2)Y6 octahedra, and edges with two equivalent N(1)Y4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-90°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to two equivalent Y(2) and two equivalent Y(3) atoms. In the second S site, S(2) is bonded to one Y(2), two equivalent Y(1), and three equivalent Y(3) atoms to form distorted SY6 octahedra that share corners with four equivalent S(2)Y6 octahedra, corners with six equivalent N(1)Y4 tetrahedra, edges with three equivalent S(2)Y6 octahedra, edges with three equivalent N(1)Y4 tetrahedra, and  a faceface with one S(2)Y6 octahedra. The corner-sharing octahedral tilt angles range from 21-50°.
Y4N2S3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Y sites. In the first Y site, Y(1) is bonded in a 2-coordinate geometry to two equivalent N(1) and four equivalent S(2) atoms. Both Y(1)-N(1) bond lengths are 2.25 Å. There are two shorter (2.87 Å) and two longer (3.00 Å) Y(1)-S(2) bond lengths. In the second Y site, Y(2) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent S(1), and two equivalent S(2) atoms. Both Y(2)-N(1) bond lengths are 2.19 Å. There is one shorter (2.73 Å) and one longer (2.77 Å) Y(2)-S(1) bond length. Both Y(2)-S(2) bond lengths are 3.27 Å. In the third Y site, Y(3) is bonded in a 6-coordinate geometry to two equivalent N(1), one S(1), and three equivalent S(2) atoms. There is one shorter (2.19 Å) and one longer (2.26 Å) Y(3)-N(1) bond length. The Y(3)-S(1) bond length is 2.85 Å. There are a spread of Y(3)-S(2) bond distances ranging from 2.83-3.28 Å. N(1) is bonded to one Y(1), one Y(2), and two equivalent Y(3) atoms to form NY4 tetrahedra that share corners with six equivalent S(2)Y6 octahedra, edges with three equivalent S(2)Y6 octahedra, and edges with two equivalent N(1)Y4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-90°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to two equivalent Y(2) and two equivalent Y(3) atoms. In the second S site, S(2) is bonded to one Y(2), two equivalent Y(1), and three equivalent Y(3) atoms to form distorted SY6 octahedra that share corners with four equivalent S(2)Y6 octahedra, corners with six equivalent N(1)Y4 tetrahedra, edges with three equivalent S(2)Y6 octahedra, edges with three equivalent N(1)Y4 tetrahedra, and  a faceface with one S(2)Y6 octahedra. The corner-sharing octahedral tilt angles range from 21-50°.