LiFeSiO4 crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(5), one O(6), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 69-74°. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 69-74°. In the third Li site, Li(3) is bonded to one O(11), one O(12), one O(7), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-73°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Si(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. In the third Fe site, Fe(3) is bonded to one O(11), one O(12), one O(3), one O(4), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Si(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the second Si site, Si(2) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the third Si site, Si(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form SiO4 tetrahedra that share corners with three equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Si(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Fe(1), and one Si(2) atom. In the third O site, O(3) is bonded to one Li(2), one Fe(1), one Fe(3), and one Si(2) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the fourth O site, O(4) is bonded to one Li(2), one Fe(1), one Fe(3), and one Si(2) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Fe(1), one Fe(2), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the sixth O site, O(6) is bonded to one Li(1), one Fe(1), one Fe(2), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(3), one Fe(3), and one Si(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(3), one Fe(2), and one Si(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(1), one Fe(3), and one Si(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(2), one Fe(2), and one Si(3) atom. In the eleventh O site, O(11) is bonded to one Li(3), one Fe(2), one Fe(3), and one Si(3) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the twelfth O site, O(12) is bonded to one Li(3), one Fe(2), one Fe(3), and one Si(3) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra.
LiFeSiO4 crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(5), one O(6), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 69-74°. The Li(1)-O(2) bond length is 1.94 Å. The Li(1)-O(5) bond length is 2.06 Å. The Li(1)-O(6) bond length is 2.17 Å. The Li(1)-O(9) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 69-74°. The Li(2)-O(1) bond length is 1.95 Å. The Li(2)-O(10) bond length is 1.94 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(4) bond length is 2.05 Å. In the third Li site, Li(3) is bonded to one O(11), one O(12), one O(7), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-73°. The Li(3)-O(11) bond length is 2.09 Å. The Li(3)-O(12) bond length is 2.12 Å. The Li(3)-O(7) bond length is 1.95 Å. The Li(3)-O(8) bond length is 1.95 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The Fe(1)-O(1) bond length is 1.96 Å. The Fe(1)-O(2) bond length is 1.95 Å. The Fe(1)-O(3) bond length is 2.11 Å. The Fe(1)-O(4) bond length is 2.14 Å. The Fe(1)-O(5) bond length is 2.10 Å. The Fe(1)-O(6) bond length is 2.12 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Si(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The Fe(2)-O(10) bond length is 1.95 Å. The Fe(2)-O(11) bond length is 2.12 Å. The Fe(2)-O(12) bond length is 2.12 Å. The Fe(2)-O(5) bond length is 2.15 Å. The Fe(2)-O(6) bond length is 2.10 Å. The Fe(2)-O(8) bond length is 1.95 Å. In the third Fe site, Fe(3) is bonded to one O(11), one O(12), one O(3), one O(4), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Si(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The Fe(3)-O(11) bond length is 2.13 Å. The Fe(3)-O(12) bond length is 2.11 Å. The Fe(3)-O(3) bond length is 2.12 Å. The Fe(3)-O(4) bond length is 2.11 Å. The Fe(3)-O(7) bond length is 1.95 Å. The Fe(3)-O(9) bond length is 1.95 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Si(1)-O(1) bond length is 1.62 Å. The Si(1)-O(5) bond length is 1.69 Å. The Si(1)-O(6) bond length is 1.68 Å. The Si(1)-O(7) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Si(2)-O(2) bond length is 1.62 Å. The Si(2)-O(3) bond length is 1.68 Å. The Si(2)-O(4) bond length is 1.69 Å. The Si(2)-O(8) bond length is 1.63 Å. In the third Si site, Si(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form SiO4 tetrahedra that share corners with three equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Si(3)-O(10) bond length is 1.62 Å. The Si(3)-O(11) bond length is 1.68 Å. The Si(3)-O(12) bond length is 1.68 Å. The Si(3)-O(9) bond length is 1.63 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Si(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Fe(1), and one Si(2) atom. In the third O site, O(3) is bonded to one Li(2), one Fe(1), one Fe(3), and one Si(2) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the fourth O site, O(4) is bonded to one Li(2), one Fe(1), one Fe(3), and one Si(2) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Fe(1), one Fe(2), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the sixth O site, O(6) is bonded to one Li(1), one Fe(1), one Fe(2), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(3), one Fe(3), and one Si(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(3), one Fe(2), and one Si(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(1), one Fe(3), and one Si(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(2), one Fe(2), and one Si(3) atom. In the eleventh O site, O(11) is bonded to one Li(3), one Fe(2), one Fe(3), and one Si(3) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra. In the twelfth O site, O(12) is bonded to one Li(3), one Fe(2), one Fe(3), and one Si(3) atom to form a mixture of distorted edge and corner-sharing OLiFe2Si tetrahedra.