LiFe2(OCl)2 is Hausmannite-derived structured and crystallizes in the monoclinic P2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent Cl(1) atoms to form distorted LiCl4 trigonal pyramids that share corners with two equivalent Fe(2)Cl2O4 octahedra, corners with four equivalent Fe(4)Cl2O4 octahedra,  an edgeedge with one Fe(2)Cl2O4 octahedra, and edges with two equivalent Li(1)Cl4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 7-80°. In the second Li site, Li(2) is bonded to two equivalent Cl(2) and two equivalent Cl(3) atoms to form distorted LiCl4 trigonal pyramids that share corners with two equivalent Fe(1)Cl2O4 octahedra, corners with two equivalent Fe(3)Cl2O4 octahedra, corners with two equivalent Fe(6)Cl2O4 octahedra,  an edgeedge with one Fe(5)Cl2O4 octahedra, and edges with two equivalent Li(3)Cl4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 5-80°. In the third Li site, Li(3) is bonded to two equivalent Cl(2) and two equivalent Cl(3) atoms to form distorted LiCl4 trigonal pyramids that share corners with two equivalent Fe(1)Cl2O4 octahedra, corners with two equivalent Fe(3)Cl2O4 octahedra, corners with two equivalent Fe(5)Cl2O4 octahedra,  an edgeedge with one Fe(6)Cl2O4 octahedra, and edges with two equivalent Li(2)Cl4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 7-76°. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(2) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(5)Cl2O4 octahedra, corners with two equivalent Li(2)Cl4 trigonal pyramids, corners with two equivalent Li(3)Cl4 trigonal pyramids, edges with two equivalent Fe(2)Cl2O4 octahedra, edges with two equivalent Fe(4)Cl2O4 octahedra, and edges with two equivalent Fe(5)Cl2O4 octahedra. The corner-sharing octahedral tilt angles are 18°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(1) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(4)Cl2O4 octahedra, corners with two equivalent Li(1)Cl4 trigonal pyramids, edges with two equivalent Fe(1)Cl2O4 octahedra, edges with two equivalent Fe(4)Cl2O4 octahedra, edges with two equivalent Fe(5)Cl2O4 octahedra, and  an edgeedge with one Li(1)Cl4 trigonal pyramid. The corner-sharing octahedral tilt angles are 17°. In the third Fe site, Fe(3) is bonded to four equivalent O(2) and two equivalent Cl(3) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(6)Cl2O4 octahedra, corners with two equivalent Li(2)Cl4 trigonal pyramids, corners with two equivalent Li(3)Cl4 trigonal pyramids, edges with two equivalent Fe(3)Cl2O4 octahedra, and edges with four equivalent Fe(6)Cl2O4 octahedra. The corner-sharing octahedral tilt angles are 18°. In the fourth Fe site, Fe(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(1) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(2)Cl2O4 octahedra, corners with four equivalent Li(1)Cl4 trigonal pyramids, edges with two equivalent Fe(1)Cl2O4 octahedra, edges with two equivalent Fe(2)Cl2O4 octahedra, and edges with two equivalent Fe(5)Cl2O4 octahedra. The corner-sharing octahedral tilt angles are 17°. In the fifth Fe site, Fe(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(2) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(1)Cl2O4 octahedra, corners with two equivalent Li(3)Cl4 trigonal pyramids, edges with two equivalent Fe(1)Cl2O4 octahedra, edges with two equivalent Fe(2)Cl2O4 octahedra, edges with two equivalent Fe(4)Cl2O4 octahedra, and  an edgeedge with one Li(2)Cl4 trigonal pyramid. The corner-sharing octahedral tilt angles are 18°. In the sixth Fe site, Fe(6) is bonded to four equivalent O(2) and two equivalent Cl(3) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(3)Cl2O4 octahedra, corners with two equivalent Li(2)Cl4 trigonal pyramids, edges with two equivalent Fe(6)Cl2O4 octahedra, edges with four equivalent Fe(3)Cl2O4 octahedra, and  an edgeedge with one Li(3)Cl4 trigonal pyramid. The corner-sharing octahedral tilt angles are 18°. There are three inequivalent O sites. In the first O site, O(3) is bonded in a see-saw-like geometry to one Fe(1), one Fe(2), one Fe(4), and one Fe(5) atom. In the second O site, O(1) is bonded in a see-saw-like geometry to one Fe(1), one Fe(2), one Fe(4), and one Fe(5) atom. In the third O site, O(2) is bonded in a see-saw-like geometry to two equivalent Fe(3) and two equivalent Fe(6) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one Fe(2), and one Fe(4) atom. In the second Cl site, Cl(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Fe(1), and one Fe(5) atom. In the third Cl site, Cl(3) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Fe(3), and one Fe(6) atom.
LiFe2(OCl)2 is Hausmannite-derived structured and crystallizes in the monoclinic P2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent Cl(1) atoms to form distorted LiCl4 trigonal pyramids that share corners with two equivalent Fe(2)Cl2O4 octahedra, corners with four equivalent Fe(4)Cl2O4 octahedra,  an edgeedge with one Fe(2)Cl2O4 octahedra, and edges with two equivalent Li(1)Cl4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 7-80°. There are two shorter (2.28 Å) and two longer (2.47 Å) Li(1)-Cl(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent Cl(2) and two equivalent Cl(3) atoms to form distorted LiCl4 trigonal pyramids that share corners with two equivalent Fe(1)Cl2O4 octahedra, corners with two equivalent Fe(3)Cl2O4 octahedra, corners with two equivalent Fe(6)Cl2O4 octahedra,  an edgeedge with one Fe(5)Cl2O4 octahedra, and edges with two equivalent Li(3)Cl4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 5-80°. Both Li(2)-Cl(2) bond lengths are 2.54 Å. Both Li(2)-Cl(3) bond lengths are 2.28 Å. In the third Li site, Li(3) is bonded to two equivalent Cl(2) and two equivalent Cl(3) atoms to form distorted LiCl4 trigonal pyramids that share corners with two equivalent Fe(1)Cl2O4 octahedra, corners with two equivalent Fe(3)Cl2O4 octahedra, corners with two equivalent Fe(5)Cl2O4 octahedra,  an edgeedge with one Fe(6)Cl2O4 octahedra, and edges with two equivalent Li(2)Cl4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 7-76°. Both Li(3)-Cl(2) bond lengths are 2.25 Å. Both Li(3)-Cl(3) bond lengths are 2.44 Å. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(2) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(5)Cl2O4 octahedra, corners with two equivalent Li(2)Cl4 trigonal pyramids, corners with two equivalent Li(3)Cl4 trigonal pyramids, edges with two equivalent Fe(2)Cl2O4 octahedra, edges with two equivalent Fe(4)Cl2O4 octahedra, and edges with two equivalent Fe(5)Cl2O4 octahedra. The corner-sharing octahedral tilt angles are 18°. Both Fe(1)-O(1) bond lengths are 2.00 Å. Both Fe(1)-O(3) bond lengths are 1.98 Å. Both Fe(1)-Cl(2) bond lengths are 2.71 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(1) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(4)Cl2O4 octahedra, corners with two equivalent Li(1)Cl4 trigonal pyramids, edges with two equivalent Fe(1)Cl2O4 octahedra, edges with two equivalent Fe(4)Cl2O4 octahedra, edges with two equivalent Fe(5)Cl2O4 octahedra, and  an edgeedge with one Li(1)Cl4 trigonal pyramid. The corner-sharing octahedral tilt angles are 17°. Both Fe(2)-O(1) bond lengths are 1.99 Å. Both Fe(2)-O(3) bond lengths are 2.01 Å. Both Fe(2)-Cl(1) bond lengths are 2.61 Å. In the third Fe site, Fe(3) is bonded to four equivalent O(2) and two equivalent Cl(3) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(6)Cl2O4 octahedra, corners with two equivalent Li(2)Cl4 trigonal pyramids, corners with two equivalent Li(3)Cl4 trigonal pyramids, edges with two equivalent Fe(3)Cl2O4 octahedra, and edges with four equivalent Fe(6)Cl2O4 octahedra. The corner-sharing octahedral tilt angles are 18°. There are two shorter (2.05 Å) and two longer (2.28 Å) Fe(3)-O(2) bond lengths. Both Fe(3)-Cl(3) bond lengths are 2.61 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(1) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(2)Cl2O4 octahedra, corners with four equivalent Li(1)Cl4 trigonal pyramids, edges with two equivalent Fe(1)Cl2O4 octahedra, edges with two equivalent Fe(2)Cl2O4 octahedra, and edges with two equivalent Fe(5)Cl2O4 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Fe(4)-O(1) bond lengths are 2.05 Å. Both Fe(4)-O(3) bond lengths are 2.25 Å. Both Fe(4)-Cl(1) bond lengths are 2.63 Å. In the fifth Fe site, Fe(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent Cl(2) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(1)Cl2O4 octahedra, corners with two equivalent Li(3)Cl4 trigonal pyramids, edges with two equivalent Fe(1)Cl2O4 octahedra, edges with two equivalent Fe(2)Cl2O4 octahedra, edges with two equivalent Fe(4)Cl2O4 octahedra, and  an edgeedge with one Li(2)Cl4 trigonal pyramid. The corner-sharing octahedral tilt angles are 18°. Both Fe(5)-O(1) bond lengths are 2.27 Å. Both Fe(5)-O(3) bond lengths are 2.06 Å. Both Fe(5)-Cl(2) bond lengths are 2.56 Å. In the sixth Fe site, Fe(6) is bonded to four equivalent O(2) and two equivalent Cl(3) atoms to form distorted FeCl2O4 octahedra that share corners with two equivalent Fe(3)Cl2O4 octahedra, corners with two equivalent Li(2)Cl4 trigonal pyramids, edges with two equivalent Fe(6)Cl2O4 octahedra, edges with four equivalent Fe(3)Cl2O4 octahedra, and  an edgeedge with one Li(3)Cl4 trigonal pyramid. The corner-sharing octahedral tilt angles are 18°. All Fe(6)-O(2) bond lengths are 2.00 Å. Both Fe(6)-Cl(3) bond lengths are 2.60 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded in a see-saw-like geometry to one Fe(1), one Fe(2), one Fe(4), and one Fe(5) atom. In the second O site, O(1) is bonded in a see-saw-like geometry to one Fe(1), one Fe(2), one Fe(4), and one Fe(5) atom. In the third O site, O(2) is bonded in a see-saw-like geometry to two equivalent Fe(3) and two equivalent Fe(6) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one Fe(2), and one Fe(4) atom. In the second Cl site, Cl(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Fe(1), and one Fe(5) atom. In the third Cl site, Cl(3) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Fe(3), and one Fe(6) atom.