LiFeSiO4 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. In the second Li site, Li(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent Fe(1)O4 tetrahedra and corners with six equivalent Si(1)O4 tetrahedra. In the third Li site, Li(3) is bonded in a trigonal planar geometry to three equivalent O(1) atoms. Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and corners with four equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 65-72°. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and corners with four equivalent Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-56°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(3), one Fe(1), and one Si(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Fe(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Si(1) atom.
LiFeSiO4 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. All Li(1)-O(2) bond lengths are 2.06 Å. All Li(1)-O(3) bond lengths are 2.45 Å. In the second Li site, Li(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent Fe(1)O4 tetrahedra and corners with six equivalent Si(1)O4 tetrahedra. All Li(2)-O(3) bond lengths are 2.63 Å. All Li(2)-O(4) bond lengths are 2.27 Å. In the third Li site, Li(3) is bonded in a trigonal planar geometry to three equivalent O(1) atoms. All Li(3)-O(1) bond lengths are 1.83 Å. Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and corners with four equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 65-72°. The Fe(1)-O(1) bond length is 1.93 Å. The Fe(1)-O(2) bond length is 1.88 Å. The Fe(1)-O(3) bond length is 1.88 Å. The Fe(1)-O(4) bond length is 1.93 Å. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and corners with four equivalent Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-56°. The Si(1)-O(1) bond length is 1.65 Å. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.65 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(3), one Fe(1), and one Si(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Fe(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Si(1) atom.