Li6Eu5Sn9 crystallizes in the orthorhombic Cmcm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Eu(3), one Sn(1), one Sn(4), and two equivalent Sn(2) atoms to form distorted edge-sharing LiEu2Sn4 tetrahedra. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one Eu(1), two equivalent Eu(3), one Sn(5), two equivalent Sn(2), and two equivalent Sn(3) atoms. In the third Li site, Li(3) is bonded in a distorted trigonal non-coplanar geometry to one Eu(1), one Eu(4), one Sn(2), and two equivalent Sn(1) atoms. There are four inequivalent Eu sites. In the first Eu site, Eu(4) is bonded in a 10-coordinate geometry to two equivalent Li(3), four equivalent Sn(1), and four equivalent Sn(4) atoms. In the second Eu site, Eu(1) is bonded in a 14-coordinate geometry to two equivalent Li(2), two equivalent Li(3), two equivalent Sn(3), four equivalent Sn(1), and four equivalent Sn(2) atoms. In the third Eu site, Eu(2) is bonded in a 9-coordinate geometry to one Sn(3), four equivalent Sn(4), and four equivalent Sn(5) atoms. In the fourth Eu site, Eu(3) is bonded in a 11-coordinate geometry to two equivalent Li(1), two equivalent Li(2), one Sn(2), two equivalent Sn(4), and four equivalent Sn(5) atoms. There are five inequivalent Sn sites. In the first Sn site, Sn(5) is bonded in a 9-coordinate geometry to one Li(2), two equivalent Eu(2), four equivalent Eu(3), one Sn(4), and one Sn(5) atom. In the second Sn site, Sn(1) is bonded in a 3-coordinate geometry to one Li(1), two equivalent Li(3), two equivalent Eu(1), two equivalent Eu(4), and one Sn(2) atom. In the third Sn site, Sn(2) is bonded in a 10-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(2), one Eu(3), two equivalent Eu(1), one Sn(1), and one Sn(3) atom. In the fourth Sn site, Sn(3) is bonded in a 4-coordinate geometry to four equivalent Li(2), one Eu(2), two equivalent Eu(1), and two equivalent Sn(2) atoms. In the fifth Sn site, Sn(4) is bonded in a 9-coordinate geometry to one Li(1), two equivalent Eu(2), two equivalent Eu(3), two equivalent Eu(4), one Sn(4), and one Sn(5) atom.
Li6Eu5Sn9 crystallizes in the orthorhombic Cmcm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Eu(3), one Sn(1), one Sn(4), and two equivalent Sn(2) atoms to form distorted edge-sharing LiEu2Sn4 tetrahedra. Both Li(1)-Eu(3) bond lengths are 3.66 Å. The Li(1)-Sn(1) bond length is 2.83 Å. The Li(1)-Sn(4) bond length is 2.85 Å. Both Li(1)-Sn(2) bond lengths are 3.05 Å. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one Eu(1), two equivalent Eu(3), one Sn(5), two equivalent Sn(2), and two equivalent Sn(3) atoms. The Li(2)-Eu(1) bond length is 3.31 Å. Both Li(2)-Eu(3) bond lengths are 3.52 Å. The Li(2)-Sn(5) bond length is 2.77 Å. Both Li(2)-Sn(2) bond lengths are 3.35 Å. Both Li(2)-Sn(3) bond lengths are 2.86 Å. In the third Li site, Li(3) is bonded in a distorted trigonal non-coplanar geometry to one Eu(1), one Eu(4), one Sn(2), and two equivalent Sn(1) atoms. The Li(3)-Eu(1) bond length is 3.52 Å. The Li(3)-Eu(4) bond length is 3.76 Å. The Li(3)-Sn(2) bond length is 2.90 Å. Both Li(3)-Sn(1) bond lengths are 2.87 Å. There are four inequivalent Eu sites. In the first Eu site, Eu(4) is bonded in a 10-coordinate geometry to two equivalent Li(3), four equivalent Sn(1), and four equivalent Sn(4) atoms. All Eu(4)-Sn(1) bond lengths are 3.59 Å. All Eu(4)-Sn(4) bond lengths are 3.47 Å. In the second Eu site, Eu(1) is bonded in a 14-coordinate geometry to two equivalent Li(2), two equivalent Li(3), two equivalent Sn(3), four equivalent Sn(1), and four equivalent Sn(2) atoms. Both Eu(1)-Sn(3) bond lengths are 3.56 Å. All Eu(1)-Sn(1) bond lengths are 3.44 Å. All Eu(1)-Sn(2) bond lengths are 3.49 Å. In the third Eu site, Eu(2) is bonded in a 9-coordinate geometry to one Sn(3), four equivalent Sn(4), and four equivalent Sn(5) atoms. The Eu(2)-Sn(3) bond length is 3.48 Å. All Eu(2)-Sn(4) bond lengths are 3.66 Å. All Eu(2)-Sn(5) bond lengths are 3.41 Å. In the fourth Eu site, Eu(3) is bonded in a 11-coordinate geometry to two equivalent Li(1), two equivalent Li(2), one Sn(2), two equivalent Sn(4), and four equivalent Sn(5) atoms. The Eu(3)-Sn(2) bond length is 3.37 Å. Both Eu(3)-Sn(4) bond lengths are 3.36 Å. There are two shorter (3.35 Å) and two longer (3.54 Å) Eu(3)-Sn(5) bond lengths. There are five inequivalent Sn sites. In the first Sn site, Sn(5) is bonded in a 9-coordinate geometry to one Li(2), two equivalent Eu(2), four equivalent Eu(3), one Sn(4), and one Sn(5) atom. The Sn(5)-Sn(4) bond length is 2.93 Å. The Sn(5)-Sn(5) bond length is 2.91 Å. In the second Sn site, Sn(1) is bonded in a 3-coordinate geometry to one Li(1), two equivalent Li(3), two equivalent Eu(1), two equivalent Eu(4), and one Sn(2) atom. The Sn(1)-Sn(2) bond length is 2.94 Å. In the third Sn site, Sn(2) is bonded in a 10-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(2), one Eu(3), two equivalent Eu(1), one Sn(1), and one Sn(3) atom. The Sn(2)-Sn(3) bond length is 2.94 Å. In the fourth Sn site, Sn(3) is bonded in a 4-coordinate geometry to four equivalent Li(2), one Eu(2), two equivalent Eu(1), and two equivalent Sn(2) atoms. In the fifth Sn site, Sn(4) is bonded in a 9-coordinate geometry to one Li(1), two equivalent Eu(2), two equivalent Eu(3), two equivalent Eu(4), one Sn(4), and one Sn(5) atom. The Sn(4)-Sn(4) bond length is 2.91 Å.