Li8CaSn7 crystallizes in the orthorhombic Cmcm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to two equivalent Li(5), one Ca(1), one Sn(2), and four equivalent Sn(5) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one Ca(1), one Sn(1), two equivalent Sn(4), and three equivalent Sn(3) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent Li(5), one Sn(1), two equivalent Sn(2), and two equivalent Sn(5) atoms. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one Li(5), one Ca(1), one Sn(2), two equivalent Sn(3), and two equivalent Sn(5) atoms. In the fifth Li site, Li(5) is bonded to two equivalent Li(1), two equivalent Li(4), four equivalent Li(3), and four equivalent Sn(5) atoms to form a mixture of face and corner-sharing LiLi8Sn4 cuboctahedra. Ca(1) is bonded in a 15-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Li(4), two equivalent Sn(4), four equivalent Sn(3), and four equivalent Sn(5) atoms. There are five inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 6-coordinate geometry to two equivalent Li(2), two equivalent Li(3), and two equivalent Sn(2) atoms. In the second Sn site, Sn(2) is bonded in a 7-coordinate geometry to one Li(1), two equivalent Li(4), four equivalent Li(3), and two equivalent Sn(1) atoms. In the third Sn site, Sn(3) is bonded in a 5-coordinate geometry to two equivalent Li(4), three equivalent Li(2), two equivalent Ca(1), and one Sn(5) atom. In the fourth Sn site, Sn(4) is bonded in a 4-coordinate geometry to four equivalent Li(2) and two equivalent Ca(1) atoms. In the fifth Sn site, Sn(5) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Li(3), two equivalent Li(4), two equivalent Li(5), two equivalent Ca(1), one Sn(3), and one Sn(5) atom.
Li8CaSn7 crystallizes in the orthorhombic Cmcm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to two equivalent Li(5), one Ca(1), one Sn(2), and four equivalent Sn(5) atoms. Both Li(1)-Li(5) bond lengths are 2.96 Å. The Li(1)-Ca(1) bond length is 3.16 Å. The Li(1)-Sn(2) bond length is 2.77 Å. All Li(1)-Sn(5) bond lengths are 2.96 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one Ca(1), one Sn(1), two equivalent Sn(4), and three equivalent Sn(3) atoms. The Li(2)-Ca(1) bond length is 3.22 Å. The Li(2)-Sn(1) bond length is 3.32 Å. Both Li(2)-Sn(4) bond lengths are 2.93 Å. There is one shorter (2.88 Å) and two longer (3.04 Å) Li(2)-Sn(3) bond lengths. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent Li(5), one Sn(1), two equivalent Sn(2), and two equivalent Sn(5) atoms. Both Li(3)-Li(5) bond lengths are 2.98 Å. The Li(3)-Sn(1) bond length is 3.28 Å. Both Li(3)-Sn(2) bond lengths are 2.87 Å. There is one shorter (2.90 Å) and one longer (2.99 Å) Li(3)-Sn(5) bond length. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one Li(5), one Ca(1), one Sn(2), two equivalent Sn(3), and two equivalent Sn(5) atoms. The Li(4)-Li(5) bond length is 3.01 Å. The Li(4)-Ca(1) bond length is 3.21 Å. The Li(4)-Sn(2) bond length is 2.81 Å. Both Li(4)-Sn(3) bond lengths are 2.91 Å. Both Li(4)-Sn(5) bond lengths are 3.08 Å. In the fifth Li site, Li(5) is bonded to two equivalent Li(1), two equivalent Li(4), four equivalent Li(3), and four equivalent Sn(5) atoms to form a mixture of face and corner-sharing LiLi8Sn4 cuboctahedra. All Li(5)-Sn(5) bond lengths are 3.23 Å. Ca(1) is bonded in a 15-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Li(4), two equivalent Sn(4), four equivalent Sn(3), and four equivalent Sn(5) atoms. Both Ca(1)-Sn(4) bond lengths are 3.46 Å. All Ca(1)-Sn(3) bond lengths are 3.38 Å. All Ca(1)-Sn(5) bond lengths are 3.42 Å. There are five inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 6-coordinate geometry to two equivalent Li(2), two equivalent Li(3), and two equivalent Sn(2) atoms. Both Sn(1)-Sn(2) bond lengths are 3.08 Å. In the second Sn site, Sn(2) is bonded in a 7-coordinate geometry to one Li(1), two equivalent Li(4), four equivalent Li(3), and two equivalent Sn(1) atoms. In the third Sn site, Sn(3) is bonded in a 5-coordinate geometry to two equivalent Li(4), three equivalent Li(2), two equivalent Ca(1), and one Sn(5) atom. The Sn(3)-Sn(5) bond length is 2.95 Å. In the fourth Sn site, Sn(4) is bonded in a 4-coordinate geometry to four equivalent Li(2) and two equivalent Ca(1) atoms. In the fifth Sn site, Sn(5) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Li(3), two equivalent Li(4), two equivalent Li(5), two equivalent Ca(1), one Sn(3), and one Sn(5) atom. The Sn(5)-Sn(5) bond length is 2.96 Å.