La4N2Te3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a distorted L-shaped geometry to two equivalent N(1), two equivalent Te(2), and three equivalent Te(1) atoms. In the second La site, La(2) is bonded in a 2-coordinate geometry to two equivalent N(1), two equivalent Te(1), and two equivalent Te(2) atoms. In the third La site, La(3) is bonded in a 2-coordinate geometry to two equivalent N(1) and four equivalent Te(1) atoms. N(1) is bonded to one La(2), one La(3), and two equivalent La(1) atoms to form NLa4 tetrahedra that share corners with four equivalent Te(2)La6 octahedra,  an edgeedge with one Te(2)La6 octahedra, and edges with two equivalent N(1)La4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-66°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to one La(2), two equivalent La(3), and three equivalent La(1) atoms. In the second Te site, Te(2) is bonded to two equivalent La(2) and four equivalent La(1) atoms to form TeLa6 octahedra that share corners with eight equivalent N(1)La4 tetrahedra, edges with two equivalent N(1)La4 tetrahedra, and faces with two equivalent Te(2)La6 octahedra.
La4N2Te3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a distorted L-shaped geometry to two equivalent N(1), two equivalent Te(2), and three equivalent Te(1) atoms. There is one shorter (2.33 Å) and one longer (2.41 Å) La(1)-N(1) bond length. There is one shorter (3.43 Å) and one longer (3.50 Å) La(1)-Te(2) bond length. There are a spread of La(1)-Te(1) bond distances ranging from 3.39-3.60 Å. In the second La site, La(2) is bonded in a 2-coordinate geometry to two equivalent N(1), two equivalent Te(1), and two equivalent Te(2) atoms. Both La(2)-N(1) bond lengths are 2.37 Å. Both La(2)-Te(1) bond lengths are 3.58 Å. There is one shorter (3.17 Å) and one longer (3.27 Å) La(2)-Te(2) bond length. In the third La site, La(3) is bonded in a 2-coordinate geometry to two equivalent N(1) and four equivalent Te(1) atoms. Both La(3)-N(1) bond lengths are 2.37 Å. There are two shorter (3.30 Å) and two longer (3.37 Å) La(3)-Te(1) bond lengths. N(1) is bonded to one La(2), one La(3), and two equivalent La(1) atoms to form NLa4 tetrahedra that share corners with four equivalent Te(2)La6 octahedra,  an edgeedge with one Te(2)La6 octahedra, and edges with two equivalent N(1)La4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-66°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to one La(2), two equivalent La(3), and three equivalent La(1) atoms. In the second Te site, Te(2) is bonded to two equivalent La(2) and four equivalent La(1) atoms to form TeLa6 octahedra that share corners with eight equivalent N(1)La4 tetrahedra, edges with two equivalent N(1)La4 tetrahedra, and faces with two equivalent Te(2)La6 octahedra.