LiBSi2 crystallizes in the tetragonal P4_2/nmc space group. Li(1) is bonded in a 11-coordinate geometry to two equivalent B(1), four equivalent Si(2), and five equivalent Si(1) atoms. B(1) is bonded to two equivalent Li(1), two equivalent Si(1), and two equivalent Si(2) atoms to form a mixture of distorted corner and edge-sharing BLi2Si4 octahedra. The corner-sharing octahedral tilt angles are 73°. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to five equivalent Li(1), two equivalent B(1), one Si(1), and one Si(2) atom. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to four equivalent Li(1), two equivalent B(1), one Si(1), and one Si(2) atom.
LiBSi2 crystallizes in the tetragonal P4_2/nmc space group. Li(1) is bonded in a 11-coordinate geometry to two equivalent B(1), four equivalent Si(2), and five equivalent Si(1) atoms. Both Li(1)-B(1) bond lengths are 2.33 Å. There are two shorter (2.72 Å) and two longer (2.79 Å) Li(1)-Si(2) bond lengths. There are a spread of Li(1)-Si(1) bond distances ranging from 2.58-2.84 Å. B(1) is bonded to two equivalent Li(1), two equivalent Si(1), and two equivalent Si(2) atoms to form a mixture of distorted corner and edge-sharing BLi2Si4 octahedra. The corner-sharing octahedral tilt angles are 73°. Both B(1)-Si(1) bond lengths are 2.07 Å. Both B(1)-Si(2) bond lengths are 2.05 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to five equivalent Li(1), two equivalent B(1), one Si(1), and one Si(2) atom. The Si(1)-Si(1) bond length is 2.46 Å. The Si(1)-Si(2) bond length is 2.44 Å. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to four equivalent Li(1), two equivalent B(1), one Si(1), and one Si(2) atom. The Si(2)-Si(2) bond length is 2.50 Å.