La4N2S3 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 6-coordinate geometry to two equivalent N(1), one S(2), and three equivalent S(1) atoms. In the second La site, La(2) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent S(1), and two equivalent S(2) atoms. N(1) is bonded to two equivalent La(1) and two equivalent La(2) atoms to form NLa4 tetrahedra that share corners with two equivalent S(2)La6 octahedra, corners with two equivalent N(1)La4 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, edges with two equivalent S(2)La6 octahedra,  an edgeedge with one N(1)La4 tetrahedra, and edges with three equivalent S(1)La5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent La(2) and three equivalent La(1) atoms to form distorted SLa5 trigonal bipyramids that share corners with five equivalent S(2)La6 octahedra, corners with four equivalent N(1)La4 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids,  an edgeedge with one S(2)La6 octahedra, edges with three equivalent N(1)La4 tetrahedra, and edges with two equivalent S(1)La5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 40-59°. In the second S site, S(2) is bonded to two equivalent La(1) and four equivalent La(2) atoms to form SLa6 octahedra that share corners with four equivalent N(1)La4 tetrahedra, corners with ten equivalent S(1)La5 trigonal bipyramids, edges with two equivalent S(2)La6 octahedra, edges with four equivalent N(1)La4 tetrahedra, and edges with two equivalent S(1)La5 trigonal bipyramids.
La4N2S3 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 6-coordinate geometry to two equivalent N(1), one S(2), and three equivalent S(1) atoms. Both La(1)-N(1) bond lengths are 2.43 Å. The La(1)-S(2) bond length is 3.05 Å. There is one shorter (3.04 Å) and two longer (3.05 Å) La(1)-S(1) bond lengths. In the second La site, La(2) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent S(1), and two equivalent S(2) atoms. There is one shorter (2.35 Å) and one longer (2.40 Å) La(2)-N(1) bond length. Both La(2)-S(1) bond lengths are 2.96 Å. Both La(2)-S(2) bond lengths are 2.95 Å. N(1) is bonded to two equivalent La(1) and two equivalent La(2) atoms to form NLa4 tetrahedra that share corners with two equivalent S(2)La6 octahedra, corners with two equivalent N(1)La4 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, edges with two equivalent S(2)La6 octahedra,  an edgeedge with one N(1)La4 tetrahedra, and edges with three equivalent S(1)La5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent La(2) and three equivalent La(1) atoms to form distorted SLa5 trigonal bipyramids that share corners with five equivalent S(2)La6 octahedra, corners with four equivalent N(1)La4 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids,  an edgeedge with one S(2)La6 octahedra, edges with three equivalent N(1)La4 tetrahedra, and edges with two equivalent S(1)La5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 40-59°. In the second S site, S(2) is bonded to two equivalent La(1) and four equivalent La(2) atoms to form SLa6 octahedra that share corners with four equivalent N(1)La4 tetrahedra, corners with ten equivalent S(1)La5 trigonal bipyramids, edges with two equivalent S(2)La6 octahedra, edges with four equivalent N(1)La4 tetrahedra, and edges with two equivalent S(1)La5 trigonal bipyramids.