Li3FeSiO5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent Si(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-15°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with four equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, and edges with four equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with four equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. Fe(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form FeO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-15°. Si(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form SiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), two equivalent Li(4), one Fe(1), and one Si(1) atom to form OLi4FeSi octahedra that share  a cornercorner with one O(3)Li3Fe2Si octahedra,  a cornercorner with one O(5)Li3Fe2Si octahedra, corners with two equivalent O(1)Li4FeSi octahedra, corners with two equivalent O(4)Li4FeSi octahedra,  an edgeedge with one O(1)Li4FeSi octahedra, edges with two equivalent O(5)Li3Fe2Si octahedra, edges with two equivalent O(4)Li4FeSi octahedra, edges with three equivalent O(3)Li3Fe2Si octahedra, and edges with four equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(5)Li3Fe2Si octahedra,  a cornercorner with one O(4)Li4FeSi octahedra, corners with two equivalent O(3)Li3Fe2Si octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(2)Li4Si2 octahedra, edges with two equivalent O(3)Li3Fe2Si octahedra, edges with two equivalent O(5)Li3Fe2Si octahedra, edges with three equivalent O(4)Li4FeSi octahedra, and edges with four equivalent O(1)Li4FeSi octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Fe(1), and one Si(1) atom to form OLi3Fe2Si octahedra that share  a cornercorner with one O(3)Li3Fe2Si octahedra,  a cornercorner with one O(1)Li4FeSi octahedra, corners with two equivalent O(5)Li3Fe2Si octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(3)Li3Fe2Si octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with three equivalent O(5)Li3Fe2Si octahedra, edges with three equivalent O(1)Li4FeSi octahedra, and edges with three equivalent O(4)Li4FeSi octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), two equivalent Li(1), one Fe(1), and one Si(1) atom to form OLi4FeSi octahedra that share  a cornercorner with one O(4)Li4FeSi octahedra,  a cornercorner with one O(2)Li4Si2 octahedra, corners with two equivalent O(5)Li3Fe2Si octahedra, corners with two equivalent O(1)Li4FeSi octahedra,  an edgeedge with one O(4)Li4FeSi octahedra, edges with two equivalent O(1)Li4FeSi octahedra, edges with three equivalent O(3)Li3Fe2Si octahedra, edges with three equivalent O(5)Li3Fe2Si octahedra, and edges with three equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(1), two equivalent Fe(1), and one Si(1) atom to form distorted OLi3Fe2Si octahedra that share  a cornercorner with one O(1)Li4FeSi octahedra,  a cornercorner with one O(2)Li4Si2 octahedra, corners with two equivalent O(3)Li3Fe2Si octahedra, corners with two equivalent O(4)Li4FeSi octahedra, edges with two equivalent O(5)Li3Fe2Si octahedra, edges with two equivalent O(1)Li4FeSi octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with three equivalent O(3)Li3Fe2Si octahedra, and edges with three equivalent O(4)Li4FeSi octahedra. The corner-sharing octahedral tilt angles range from 3-12°.
Li3FeSiO5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent Si(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-15°. The Li(1)-O(2) bond length is 2.23 Å. The Li(1)-O(3) bond length is 2.25 Å. There is one shorter (2.06 Å) and one longer (2.29 Å) Li(1)-O(4) bond length. There is one shorter (2.06 Å) and one longer (2.09 Å) Li(1)-O(5) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with four equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, and edges with four equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. Both Li(2)-O(1) bond lengths are 2.30 Å. Both Li(2)-O(2) bond lengths are 2.22 Å. Both Li(2)-O(3) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with four equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. Both Li(3)-O(1) bond lengths are 2.06 Å. Both Li(3)-O(2) bond lengths are 2.08 Å. Both Li(3)-O(4) bond lengths are 2.10 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The Li(4)-O(2) bond length is 2.06 Å. The Li(4)-O(3) bond length is 2.10 Å. The Li(4)-O(4) bond length is 2.06 Å. The Li(4)-O(5) bond length is 2.41 Å. There is one shorter (2.02 Å) and one longer (2.06 Å) Li(4)-O(1) bond length. Fe(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form FeO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-15°. The Fe(1)-O(1) bond length is 1.97 Å. The Fe(1)-O(4) bond length is 1.97 Å. There is one shorter (2.04 Å) and one longer (2.14 Å) Fe(1)-O(3) bond length. There is one shorter (2.03 Å) and one longer (2.09 Å) Fe(1)-O(5) bond length. Si(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form SiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. The Si(1)-O(1) bond length is 1.82 Å. The Si(1)-O(3) bond length is 1.86 Å. The Si(1)-O(4) bond length is 1.83 Å. The Si(1)-O(5) bond length is 1.85 Å. Both Si(1)-O(2) bond lengths are 1.83 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), two equivalent Li(4), one Fe(1), and one Si(1) atom to form OLi4FeSi octahedra that share  a cornercorner with one O(3)Li3Fe2Si octahedra,  a cornercorner with one O(5)Li3Fe2Si octahedra, corners with two equivalent O(1)Li4FeSi octahedra, corners with two equivalent O(4)Li4FeSi octahedra,  an edgeedge with one O(1)Li4FeSi octahedra, edges with two equivalent O(5)Li3Fe2Si octahedra, edges with two equivalent O(4)Li4FeSi octahedra, edges with three equivalent O(3)Li3Fe2Si octahedra, and edges with four equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(5)Li3Fe2Si octahedra,  a cornercorner with one O(4)Li4FeSi octahedra, corners with two equivalent O(3)Li3Fe2Si octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(2)Li4Si2 octahedra, edges with two equivalent O(3)Li3Fe2Si octahedra, edges with two equivalent O(5)Li3Fe2Si octahedra, edges with three equivalent O(4)Li4FeSi octahedra, and edges with four equivalent O(1)Li4FeSi octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Fe(1), and one Si(1) atom to form OLi3Fe2Si octahedra that share  a cornercorner with one O(3)Li3Fe2Si octahedra,  a cornercorner with one O(1)Li4FeSi octahedra, corners with two equivalent O(5)Li3Fe2Si octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(3)Li3Fe2Si octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with three equivalent O(5)Li3Fe2Si octahedra, edges with three equivalent O(1)Li4FeSi octahedra, and edges with three equivalent O(4)Li4FeSi octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), two equivalent Li(1), one Fe(1), and one Si(1) atom to form OLi4FeSi octahedra that share  a cornercorner with one O(4)Li4FeSi octahedra,  a cornercorner with one O(2)Li4Si2 octahedra, corners with two equivalent O(5)Li3Fe2Si octahedra, corners with two equivalent O(1)Li4FeSi octahedra,  an edgeedge with one O(4)Li4FeSi octahedra, edges with two equivalent O(1)Li4FeSi octahedra, edges with three equivalent O(3)Li3Fe2Si octahedra, edges with three equivalent O(5)Li3Fe2Si octahedra, and edges with three equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(1), two equivalent Fe(1), and one Si(1) atom to form distorted OLi3Fe2Si octahedra that share  a cornercorner with one O(1)Li4FeSi octahedra,  a cornercorner with one O(2)Li4Si2 octahedra, corners with two equivalent O(3)Li3Fe2Si octahedra, corners with two equivalent O(4)Li4FeSi octahedra, edges with two equivalent O(5)Li3Fe2Si octahedra, edges with two equivalent O(1)Li4FeSi octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with three equivalent O(3)Li3Fe2Si octahedra, and edges with three equivalent O(4)Li4FeSi octahedra. The corner-sharing octahedral tilt angles range from 3-12°.