Eu4Li7Bi6 crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Li(4), two equivalent Eu(2), one Bi(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted LiLiEu2Bi4 tetrahedra that share corners with two equivalent Eu(1)LiBi6 octahedra,  a cornercorner with one Li(1)LiEu2Bi4 tetrahedra, corners with three equivalent Li(2)Eu3Bi4 tetrahedra, edges with three equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Li(1)LiEu2Bi4 tetrahedra,  a faceface with one Eu(1)LiBi6 octahedra,  a faceface with one Li(2)Eu3Bi4 tetrahedra, and faces with two equivalent Li(3)Li2EuBi4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. In the second Li site, Li(2) is bonded to three equivalent Eu(2), one Bi(1), and three equivalent Bi(2) atoms to form distorted LiEu3Bi4 tetrahedra that share  a cornercorner with one Eu(1)LiBi6 octahedra, corners with two equivalent Li(3)Li2EuBi4 tetrahedra, corners with three equivalent Li(1)LiEu2Bi4 tetrahedra, edges with two equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Li(1)LiEu2Bi4 tetrahedra,  a faceface with one Li(3)Li2EuBi4 tetrahedra,  a faceface with one Li(1)LiEu2Bi4 tetrahedra, and faces with two equivalent Li(2)Eu3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the third Li site, Li(3) is bonded to two equivalent Li(4), one Eu(2), two equivalent Bi(2), and two equivalent Bi(3) atoms to form distorted LiLi2EuBi4 tetrahedra that share corners with two equivalent Eu(1)LiBi6 octahedra, corners with two equivalent Li(2)Eu3Bi4 tetrahedra, corners with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Li(1)LiEu2Bi4 tetrahedra, faces with two equivalent Eu(1)LiBi6 octahedra,  a faceface with one Li(2)Eu3Bi4 tetrahedra,  a faceface with one Li(3)Li2EuBi4 tetrahedra, and faces with two equivalent Li(1)LiEu2Bi4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-48°. In the fourth Li site, Li(4) is bonded in a 14-coordinate geometry to two equivalent Li(1), four equivalent Li(3), two equivalent Eu(1), two equivalent Bi(2), and four equivalent Bi(3) atoms. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded to one Li(4), one Bi(2), two equivalent Bi(1), and three equivalent Bi(3) atoms to form distorted EuLiBi6 octahedra that share  a cornercorner with one Eu(1)LiBi6 octahedra,  a cornercorner with one Li(2)Eu3Bi4 tetrahedra, corners with two equivalent Li(3)Li2EuBi4 tetrahedra, corners with two equivalent Li(1)LiEu2Bi4 tetrahedra, edges with four equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with three equivalent Li(1)LiEu2Bi4 tetrahedra,  a faceface with one Li(1)LiEu2Bi4 tetrahedra, and faces with two equivalent Li(3)Li2EuBi4 tetrahedra. The corner-sharing octahedra are not tilted. In the second Eu site, Eu(2) is bonded in a 12-coordinate geometry to one Li(3), two equivalent Li(1), three equivalent Li(2), two equivalent Bi(2), and four equivalent Bi(1) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to one Li(1), one Li(2), two equivalent Eu(1), four equivalent Eu(2), and one Bi(1) atom. In the second Bi site, Bi(2) is bonded in a 10-coordinate geometry to one Li(1), one Li(4), two equivalent Li(3), three equivalent Li(2), one Eu(1), and two equivalent Eu(2) atoms. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(3), two equivalent Li(4), and three equivalent Eu(1) atoms.
Eu4Li7Bi6 crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Li(4), two equivalent Eu(2), one Bi(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted LiLiEu2Bi4 tetrahedra that share corners with two equivalent Eu(1)LiBi6 octahedra,  a cornercorner with one Li(1)LiEu2Bi4 tetrahedra, corners with three equivalent Li(2)Eu3Bi4 tetrahedra, edges with three equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Li(1)LiEu2Bi4 tetrahedra,  a faceface with one Eu(1)LiBi6 octahedra,  a faceface with one Li(2)Eu3Bi4 tetrahedra, and faces with two equivalent Li(3)Li2EuBi4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. The Li(1)-Li(4) bond length is 2.93 Å. Both Li(1)-Eu(2) bond lengths are 3.45 Å. The Li(1)-Bi(1) bond length is 2.91 Å. The Li(1)-Bi(2) bond length is 2.95 Å. Both Li(1)-Bi(3) bond lengths are 2.84 Å. In the second Li site, Li(2) is bonded to three equivalent Eu(2), one Bi(1), and three equivalent Bi(2) atoms to form distorted LiEu3Bi4 tetrahedra that share  a cornercorner with one Eu(1)LiBi6 octahedra, corners with two equivalent Li(3)Li2EuBi4 tetrahedra, corners with three equivalent Li(1)LiEu2Bi4 tetrahedra, edges with two equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Li(1)LiEu2Bi4 tetrahedra,  a faceface with one Li(3)Li2EuBi4 tetrahedra,  a faceface with one Li(1)LiEu2Bi4 tetrahedra, and faces with two equivalent Li(2)Eu3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. There is one shorter (3.44 Å) and two longer (3.46 Å) Li(2)-Eu(2) bond lengths. The Li(2)-Bi(1) bond length is 2.90 Å. There are two shorter (2.87 Å) and one longer (2.91 Å) Li(2)-Bi(2) bond length. In the third Li site, Li(3) is bonded to two equivalent Li(4), one Eu(2), two equivalent Bi(2), and two equivalent Bi(3) atoms to form distorted LiLi2EuBi4 tetrahedra that share corners with two equivalent Eu(1)LiBi6 octahedra, corners with two equivalent Li(2)Eu3Bi4 tetrahedra, corners with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with two equivalent Li(1)LiEu2Bi4 tetrahedra, faces with two equivalent Eu(1)LiBi6 octahedra,  a faceface with one Li(2)Eu3Bi4 tetrahedra,  a faceface with one Li(3)Li2EuBi4 tetrahedra, and faces with two equivalent Li(1)LiEu2Bi4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-48°. Both Li(3)-Li(4) bond lengths are 2.93 Å. The Li(3)-Eu(2) bond length is 3.46 Å. Both Li(3)-Bi(2) bond lengths are 2.93 Å. There is one shorter (2.86 Å) and one longer (2.87 Å) Li(3)-Bi(3) bond length. In the fourth Li site, Li(4) is bonded in a 14-coordinate geometry to two equivalent Li(1), four equivalent Li(3), two equivalent Eu(1), two equivalent Bi(2), and four equivalent Bi(3) atoms. Both Li(4)-Eu(1) bond lengths are 3.76 Å. Both Li(4)-Bi(2) bond lengths are 3.30 Å. All Li(4)-Bi(3) bond lengths are 3.36 Å. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded to one Li(4), one Bi(2), two equivalent Bi(1), and three equivalent Bi(3) atoms to form distorted EuLiBi6 octahedra that share  a cornercorner with one Eu(1)LiBi6 octahedra,  a cornercorner with one Li(2)Eu3Bi4 tetrahedra, corners with two equivalent Li(3)Li2EuBi4 tetrahedra, corners with two equivalent Li(1)LiEu2Bi4 tetrahedra, edges with four equivalent Eu(1)LiBi6 octahedra, edges with two equivalent Li(2)Eu3Bi4 tetrahedra, edges with two equivalent Li(3)Li2EuBi4 tetrahedra, edges with three equivalent Li(1)LiEu2Bi4 tetrahedra,  a faceface with one Li(1)LiEu2Bi4 tetrahedra, and faces with two equivalent Li(3)Li2EuBi4 tetrahedra. The corner-sharing octahedra are not tilted. The Eu(1)-Bi(2) bond length is 3.41 Å. Both Eu(1)-Bi(1) bond lengths are 3.40 Å. There are two shorter (3.34 Å) and one longer (3.38 Å) Eu(1)-Bi(3) bond length. In the second Eu site, Eu(2) is bonded in a 12-coordinate geometry to one Li(3), two equivalent Li(1), three equivalent Li(2), two equivalent Bi(2), and four equivalent Bi(1) atoms. Both Eu(2)-Bi(2) bond lengths are 3.47 Å. There are two shorter (3.51 Å) and two longer (3.53 Å) Eu(2)-Bi(1) bond lengths. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to one Li(1), one Li(2), two equivalent Eu(1), four equivalent Eu(2), and one Bi(1) atom. The Bi(1)-Bi(1) bond length is 3.08 Å. In the second Bi site, Bi(2) is bonded in a 10-coordinate geometry to one Li(1), one Li(4), two equivalent Li(3), three equivalent Li(2), one Eu(1), and two equivalent Eu(2) atoms. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(3), two equivalent Li(4), and three equivalent Eu(1) atoms.