Bi4N2Te3 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted L-shaped geometry to two equivalent N(1), two equivalent Te(1), and two equivalent Te(2) atoms. In the second Bi site, Bi(2) is bonded in a distorted bent 120 degrees geometry to two equivalent N(1), one Te(1), and three equivalent Te(2) atoms. N(1) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form NBi4 tetrahedra that share corners with two equivalent Te(1)Bi6 octahedra, corners with two equivalent N(1)Bi4 tetrahedra, edges with two equivalent Te(1)Bi6 octahedra, and  an edgeedge with one N(1)Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 42°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Bi(2) and four equivalent Bi(1) atoms to form distorted TeBi6 octahedra that share corners with four equivalent N(1)Bi4 tetrahedra, edges with two equivalent Te(1)Bi6 octahedra, and edges with four equivalent N(1)Bi4 tetrahedra. In the second Te site, Te(2) is bonded in a 5-coordinate geometry to two equivalent Bi(1) and three equivalent Bi(2) atoms.
Bi4N2Te3 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted L-shaped geometry to two equivalent N(1), two equivalent Te(1), and two equivalent Te(2) atoms. There is one shorter (2.32 Å) and one longer (2.33 Å) Bi(1)-N(1) bond length. Both Bi(1)-Te(1) bond lengths are 3.29 Å. Both Bi(1)-Te(2) bond lengths are 3.30 Å. In the second Bi site, Bi(2) is bonded in a distorted bent 120 degrees geometry to two equivalent N(1), one Te(1), and three equivalent Te(2) atoms. Both Bi(2)-N(1) bond lengths are 2.47 Å. The Bi(2)-Te(1) bond length is 3.26 Å. There is one shorter (3.05 Å) and two longer (3.27 Å) Bi(2)-Te(2) bond lengths. N(1) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form NBi4 tetrahedra that share corners with two equivalent Te(1)Bi6 octahedra, corners with two equivalent N(1)Bi4 tetrahedra, edges with two equivalent Te(1)Bi6 octahedra, and  an edgeedge with one N(1)Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 42°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Bi(2) and four equivalent Bi(1) atoms to form distorted TeBi6 octahedra that share corners with four equivalent N(1)Bi4 tetrahedra, edges with two equivalent Te(1)Bi6 octahedra, and edges with four equivalent N(1)Bi4 tetrahedra. In the second Te site, Te(2) is bonded in a 5-coordinate geometry to two equivalent Bi(1) and three equivalent Bi(2) atoms.