Li7Si2 is zeta silver zinc-like structured and crystallizes in the orthorhombic Pbam space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent Li(8) and four equivalent Si(1) atoms. In the second Li site, Li(2) is bonded in a distorted body-centered cubic geometry to two equivalent Li(3), two equivalent Li(4), and four equivalent Li(6) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one Li(2), two equivalent Li(5), two equivalent Li(8), one Si(1), and two equivalent Si(2) atoms. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(5), two equivalent Si(1), and two equivalent Si(2) atoms. In the fifth Li site, Li(5) is bonded in a 10-coordinate geometry to one Li(4), two equivalent Li(3), two equivalent Li(7), two equivalent Li(8), one Si(1), and two equivalent Si(2) atoms. In the sixth Li site, Li(6) is bonded in a 2-coordinate geometry to one Li(8), two equivalent Li(2), two equivalent Si(1), and two equivalent Si(2) atoms. In the seventh Li site, Li(7) is bonded in a 2-coordinate geometry to two equivalent Li(5), two equivalent Li(8), and two equivalent Si(2) atoms. In the eighth Li site, Li(8) is bonded in a 12-coordinate geometry to one Li(1), one Li(6), two equivalent Li(3), two equivalent Li(5), two equivalent Li(7), two equivalent Si(1), and two equivalent Si(2) atoms. There are two inequivalent Si sites. In the first Si site, Si(2) is bonded in a 12-coordinate geometry to two equivalent Li(3), two equivalent Li(4), two equivalent Li(5), two equivalent Li(6), two equivalent Li(7), and two equivalent Li(8) atoms. In the second Si site, Si(1) is bonded in a 11-coordinate geometry to one Li(3), one Li(5), two equivalent Li(1), two equivalent Li(4), two equivalent Li(6), two equivalent Li(8), and one Si(1) atom.
Li7Si2 is zeta silver zinc-like structured and crystallizes in the orthorhombic Pbam space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent Li(8) and four equivalent Si(1) atoms. Both Li(1)-Li(8) bond lengths are 2.94 Å. All Li(1)-Si(1) bond lengths are 2.56 Å. In the second Li site, Li(2) is bonded in a distorted body-centered cubic geometry to two equivalent Li(3), two equivalent Li(4), and four equivalent Li(6) atoms. Both Li(2)-Li(3) bond lengths are 2.34 Å. Both Li(2)-Li(4) bond lengths are 2.61 Å. All Li(2)-Li(6) bond lengths are 2.64 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one Li(2), two equivalent Li(5), two equivalent Li(8), one Si(1), and two equivalent Si(2) atoms. There is one shorter (2.36 Å) and one longer (2.77 Å) Li(3)-Li(5) bond length. Both Li(3)-Li(8) bond lengths are 2.66 Å. The Li(3)-Si(1) bond length is 2.53 Å. Both Li(3)-Si(2) bond lengths are 2.65 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(5), two equivalent Si(1), and two equivalent Si(2) atoms. The Li(4)-Li(5) bond length is 2.73 Å. There is one shorter (2.69 Å) and one longer (2.73 Å) Li(4)-Si(1) bond length. Both Li(4)-Si(2) bond lengths are 2.88 Å. In the fifth Li site, Li(5) is bonded in a 10-coordinate geometry to one Li(4), two equivalent Li(3), two equivalent Li(7), two equivalent Li(8), one Si(1), and two equivalent Si(2) atoms. Both Li(5)-Li(7) bond lengths are 2.86 Å. Both Li(5)-Li(8) bond lengths are 2.68 Å. The Li(5)-Si(1) bond length is 2.65 Å. Both Li(5)-Si(2) bond lengths are 2.72 Å. In the sixth Li site, Li(6) is bonded in a 2-coordinate geometry to one Li(8), two equivalent Li(2), two equivalent Si(1), and two equivalent Si(2) atoms. The Li(6)-Li(8) bond length is 2.46 Å. Both Li(6)-Si(1) bond lengths are 2.96 Å. There is one shorter (2.65 Å) and one longer (2.80 Å) Li(6)-Si(2) bond length. In the seventh Li site, Li(7) is bonded in a 2-coordinate geometry to two equivalent Li(5), two equivalent Li(8), and two equivalent Si(2) atoms. There is one shorter (2.57 Å) and one longer (2.61 Å) Li(7)-Li(8) bond length. There is one shorter (2.66 Å) and one longer (2.72 Å) Li(7)-Si(2) bond length. In the eighth Li site, Li(8) is bonded in a 12-coordinate geometry to one Li(1), one Li(6), two equivalent Li(3), two equivalent Li(5), two equivalent Li(7), two equivalent Si(1), and two equivalent Si(2) atoms. Both Li(8)-Si(1) bond lengths are 2.81 Å. There is one shorter (2.85 Å) and one longer (2.93 Å) Li(8)-Si(2) bond length. There are two inequivalent Si sites. In the first Si site, Si(2) is bonded in a 12-coordinate geometry to two equivalent Li(3), two equivalent Li(4), two equivalent Li(5), two equivalent Li(6), two equivalent Li(7), and two equivalent Li(8) atoms. In the second Si site, Si(1) is bonded in a 11-coordinate geometry to one Li(3), one Li(5), two equivalent Li(1), two equivalent Li(4), two equivalent Li(6), two equivalent Li(8), and one Si(1) atom. The Si(1)-Si(1) bond length is 2.50 Å.