Li2Sm2Si3 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to three equivalent Sm(2), one Si(1), and three equivalent Si(2) atoms to form a mixture of distorted edge, face, and corner-sharing LiSm3Si4 tetrahedra. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 9-coordinate geometry to one Si(2) and eight equivalent Si(1) atoms. In the second Sm site, Sm(2) is bonded in a 12-coordinate geometry to six equivalent Li(1), two equivalent Si(2), and four equivalent Si(1) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to one Li(1), two equivalent Sm(2), four equivalent Sm(1), and two equivalent Si(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to six equivalent Li(1), one Sm(1), and two equivalent Sm(2) atoms.
Li2Sm2Si3 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to three equivalent Sm(2), one Si(1), and three equivalent Si(2) atoms to form a mixture of distorted edge, face, and corner-sharing LiSm3Si4 tetrahedra. There are two shorter (3.07 Å) and one longer (3.08 Å) Li(1)-Sm(2) bond length. The Li(1)-Si(1) bond length is 2.57 Å. There are two shorter (2.59 Å) and one longer (2.68 Å) Li(1)-Si(2) bond length. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 9-coordinate geometry to one Si(2) and eight equivalent Si(1) atoms. The Sm(1)-Si(2) bond length is 3.06 Å. There are four shorter (3.10 Å) and four longer (3.20 Å) Sm(1)-Si(1) bond lengths. In the second Sm site, Sm(2) is bonded in a 12-coordinate geometry to six equivalent Li(1), two equivalent Si(2), and four equivalent Si(1) atoms. Both Sm(2)-Si(2) bond lengths are 3.12 Å. All Sm(2)-Si(1) bond lengths are 3.08 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to one Li(1), two equivalent Sm(2), four equivalent Sm(1), and two equivalent Si(1) atoms. There is one shorter (2.35 Å) and one longer (2.37 Å) Si(1)-Si(1) bond length. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to six equivalent Li(1), one Sm(1), and two equivalent Sm(2) atoms.