Na(LiSi2)3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Li(2), one Si(1), one Si(6), two equivalent Si(2), two equivalent Si(3), and two equivalent Si(4) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Si(3), one Si(5), and three equivalent Si(2) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Si(2), two equivalent Si(5), and three equivalent Si(4) atoms. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one Si(2), two equivalent Si(1), two equivalent Si(3), two equivalent Si(5), and two equivalent Si(6) atoms. There are six inequivalent Si sites. In the first Si site, Si(5) is bonded in a 9-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Li(3), one Si(4), one Si(6), and two equivalent Si(2) atoms. In the second Si site, Si(6) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Li(3), one Si(1), one Si(5), and two equivalent Si(3) atoms. In the third Si site, Si(1) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Li(3), one Si(3), one Si(6), and two equivalent Si(4) atoms. In the fourth Si site, Si(2) is bonded in a 9-coordinate geometry to two equivalent Na(1), one Li(2), one Li(3), three equivalent Li(1), and two equivalent Si(5) atoms. In the fifth Si site, Si(3) is bonded in a 8-coordinate geometry to two equivalent Na(1), one Li(1), two equivalent Li(3), one Si(1), and two equivalent Si(6) atoms. In the sixth Si site, Si(4) is bonded in a 8-coordinate geometry to two equivalent Na(1), three equivalent Li(2), one Si(5), and two equivalent Si(1) atoms.
Na(LiSi2)3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Li(2), one Si(1), one Si(6), two equivalent Si(2), two equivalent Si(3), and two equivalent Si(4) atoms. Both Na(1)-Li(1) bond lengths are 3.08 Å. Both Na(1)-Li(2) bond lengths are 3.12 Å. The Na(1)-Si(1) bond length is 3.20 Å. The Na(1)-Si(6) bond length is 3.13 Å. Both Na(1)-Si(2) bond lengths are 3.14 Å. Both Na(1)-Si(3) bond lengths are 3.21 Å. Both Na(1)-Si(4) bond lengths are 3.32 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Si(3), one Si(5), and three equivalent Si(2) atoms. The Li(1)-Si(3) bond length is 2.79 Å. The Li(1)-Si(5) bond length is 2.96 Å. There are two shorter (2.68 Å) and one longer (2.69 Å) Li(1)-Si(2) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Si(2), two equivalent Si(5), and three equivalent Si(4) atoms. The Li(2)-Si(2) bond length is 2.55 Å. Both Li(2)-Si(5) bond lengths are 2.94 Å. There are two shorter (2.66 Å) and one longer (2.80 Å) Li(2)-Si(4) bond length. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one Si(2), two equivalent Si(1), two equivalent Si(3), two equivalent Si(5), and two equivalent Si(6) atoms. The Li(3)-Si(2) bond length is 2.62 Å. Both Li(3)-Si(1) bond lengths are 2.85 Å. Both Li(3)-Si(3) bond lengths are 2.84 Å. Both Li(3)-Si(5) bond lengths are 3.06 Å. Both Li(3)-Si(6) bond lengths are 2.89 Å. There are six inequivalent Si sites. In the first Si site, Si(5) is bonded in a 9-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Li(3), one Si(4), one Si(6), and two equivalent Si(2) atoms. The Si(5)-Si(4) bond length is 2.45 Å. The Si(5)-Si(6) bond length is 2.41 Å. Both Si(5)-Si(2) bond lengths are 2.41 Å. In the second Si site, Si(6) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Li(3), one Si(1), one Si(5), and two equivalent Si(3) atoms. The Si(6)-Si(1) bond length is 2.45 Å. Both Si(6)-Si(3) bond lengths are 2.39 Å. In the third Si site, Si(1) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Li(3), one Si(3), one Si(6), and two equivalent Si(4) atoms. The Si(1)-Si(3) bond length is 2.45 Å. Both Si(1)-Si(4) bond lengths are 2.38 Å. In the fourth Si site, Si(2) is bonded in a 9-coordinate geometry to two equivalent Na(1), one Li(2), one Li(3), three equivalent Li(1), and two equivalent Si(5) atoms. In the fifth Si site, Si(3) is bonded in a 8-coordinate geometry to two equivalent Na(1), one Li(1), two equivalent Li(3), one Si(1), and two equivalent Si(6) atoms. In the sixth Si site, Si(4) is bonded in a 8-coordinate geometry to two equivalent Na(1), three equivalent Li(2), one Si(5), and two equivalent Si(1) atoms.