Li13Si4 crystallizes in the orthorhombic Pbam space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one Li(2), two equivalent Si(1), and two equivalent Si(2) atoms. In the second Li site, Li(2) is bonded in a 11-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(7), two equivalent Li(3), one Si(2), and four equivalent Si(1) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to two equivalent Li(2), two equivalent Si(1), and two equivalent Si(2) atoms. In the fourth Li site, Li(4) is bonded in a 2-coordinate geometry to one Li(2) and two equivalent Si(2) atoms. In the fifth Li site, Li(5) is bonded in a distorted trigonal planar geometry to one Si(1) and two equivalent Si(2) atoms. In the sixth Li site, Li(6) is bonded in a 3-coordinate geometry to one Si(1) and two equivalent Si(2) atoms. In the seventh Li site, Li(7) is bonded in a linear geometry to two equivalent Li(2) and two equivalent Si(2) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 11-coordinate geometry to one Li(5), one Li(6), two equivalent Li(1), two equivalent Li(3), four equivalent Li(2), and one Si(1) atom. In the second Si site, Si(2) is bonded in a 12-coordinate geometry to one Li(2), one Li(7), two equivalent Li(1), two equivalent Li(3), two equivalent Li(4), two equivalent Li(5), and two equivalent Li(6) atoms.
Li13Si4 crystallizes in the orthorhombic Pbam space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one Li(2), two equivalent Si(1), and two equivalent Si(2) atoms. The Li(1)-Li(2) bond length is 2.78 Å. Both Li(1)-Si(1) bond lengths are 2.85 Å. There is one shorter (2.78 Å) and one longer (3.01 Å) Li(1)-Si(2) bond length. In the second Li site, Li(2) is bonded in a 11-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(7), two equivalent Li(3), one Si(2), and four equivalent Si(1) atoms. The Li(2)-Li(2) bond length is 2.53 Å. The Li(2)-Li(4) bond length is 2.57 Å. The Li(2)-Li(7) bond length is 2.77 Å. Both Li(2)-Li(3) bond lengths are 2.58 Å. The Li(2)-Si(2) bond length is 2.91 Å. There are two shorter (2.69 Å) and two longer (2.91 Å) Li(2)-Si(1) bond lengths. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to two equivalent Li(2), two equivalent Si(1), and two equivalent Si(2) atoms. There is one shorter (2.64 Å) and one longer (2.87 Å) Li(3)-Si(1) bond length. Both Li(3)-Si(2) bond lengths are 2.72 Å. In the fourth Li site, Li(4) is bonded in a 2-coordinate geometry to one Li(2) and two equivalent Si(2) atoms. Both Li(4)-Si(2) bond lengths are 2.60 Å. In the fifth Li site, Li(5) is bonded in a distorted trigonal planar geometry to one Si(1) and two equivalent Si(2) atoms. The Li(5)-Si(1) bond length is 2.64 Å. Both Li(5)-Si(2) bond lengths are 2.63 Å. In the sixth Li site, Li(6) is bonded in a 3-coordinate geometry to one Si(1) and two equivalent Si(2) atoms. The Li(6)-Si(1) bond length is 2.70 Å. Both Li(6)-Si(2) bond lengths are 2.73 Å. In the seventh Li site, Li(7) is bonded in a linear geometry to two equivalent Li(2) and two equivalent Si(2) atoms. Both Li(7)-Si(2) bond lengths are 2.49 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 11-coordinate geometry to one Li(5), one Li(6), two equivalent Li(1), two equivalent Li(3), four equivalent Li(2), and one Si(1) atom. The Si(1)-Si(1) bond length is 2.36 Å. In the second Si site, Si(2) is bonded in a 12-coordinate geometry to one Li(2), one Li(7), two equivalent Li(1), two equivalent Li(3), two equivalent Li(4), two equivalent Li(5), and two equivalent Li(6) atoms.