Li4CrFe3Sn2(PO4)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(24), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(17), and one O(21) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. In the third Li site, Li(3) is bonded to one O(15), one O(22), one O(23), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. In the fourth Li site, Li(4) is bonded to one O(18), one O(19), one O(2), and one O(24) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. Cr(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(22), and one O(5) atom to form CrO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(20), one O(3), one O(7), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(8) atom. In the third Fe site, Fe(3) is bonded to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 3-coordinate geometry to one O(14), one O(3), and one O(7) atom. In the second Sn site, Sn(2) is bonded in a 3-coordinate geometry to one O(10), one O(6), and one O(8) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(14), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-51°. In the second P site, P(2) is bonded to one O(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-50°. In the third P site, P(3) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-45°. In the fourth P site, P(4) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-46°. In the fifth P site, P(5) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-51°. In the sixth P site, P(6) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-51°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one Fe(2), and one P(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(4), one Fe(2), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Fe(1), one Sn(1), and one P(5) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Fe(2), and one P(3) atom to form distorted corner-sharing OLi2FeP tetrahedra. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Sn(2), and one P(5) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Sn(1), and one P(6) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Sn(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), one Sn(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Li(2), one Cr(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a linear geometry to one Cr(1) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Sn(1), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Li(2), one Fe(3), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one Li(4), one Cr(1), and one P(3) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(4), one Fe(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Fe(3), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(3), one Cr(1), and one P(4) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(1) atom. In the twenty-fourth O site, O(24) is bonded to one Li(1), one Li(4), one Fe(3), and one P(5) atom to form distorted corner-sharing OLi2FeP tetrahedra.
Li4CrFe3Sn2(PO4)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(24), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.45 Å. The Li(1)-O(14) bond length is 2.07 Å. The Li(1)-O(24) bond length is 2.31 Å. The Li(1)-O(4) bond length is 2.04 Å. The Li(1)-O(8) bond length is 1.98 Å. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(17), and one O(21) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. The Li(2)-O(1) bond length is 1.98 Å. The Li(2)-O(11) bond length is 2.02 Å. The Li(2)-O(17) bond length is 1.94 Å. The Li(2)-O(21) bond length is 2.10 Å. In the third Li site, Li(3) is bonded to one O(15), one O(22), one O(23), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. The Li(3)-O(15) bond length is 1.96 Å. The Li(3)-O(22) bond length is 2.07 Å. The Li(3)-O(23) bond length is 2.08 Å. The Li(3)-O(4) bond length is 2.14 Å. In the fourth Li site, Li(4) is bonded to one O(18), one O(19), one O(2), and one O(24) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. The Li(4)-O(18) bond length is 2.05 Å. The Li(4)-O(19) bond length is 1.93 Å. The Li(4)-O(2) bond length is 1.99 Å. The Li(4)-O(24) bond length is 2.25 Å. Cr(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(22), and one O(5) atom to form CrO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Cr(1)-O(11) bond length is 2.05 Å. The Cr(1)-O(13) bond length is 1.98 Å. The Cr(1)-O(16) bond length is 2.01 Å. The Cr(1)-O(18) bond length is 2.06 Å. The Cr(1)-O(22) bond length is 2.06 Å. The Cr(1)-O(5) bond length is 2.01 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(20), one O(3), one O(7), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(1)-O(12) bond length is 1.93 Å. The Fe(1)-O(14) bond length is 2.22 Å. The Fe(1)-O(20) bond length is 1.93 Å. The Fe(1)-O(3) bond length is 2.12 Å. The Fe(1)-O(7) bond length is 2.15 Å. The Fe(1)-O(9) bond length is 1.91 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(8) atom. The Fe(2)-O(1) bond length is 2.06 Å. The Fe(2)-O(10) bond length is 2.25 Å. The Fe(2)-O(2) bond length is 2.09 Å. The Fe(2)-O(4) bond length is 2.24 Å. The Fe(2)-O(6) bond length is 2.22 Å. The Fe(2)-O(8) bond length is 2.50 Å. In the third Fe site, Fe(3) is bonded to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The Fe(3)-O(15) bond length is 2.13 Å. The Fe(3)-O(17) bond length is 2.16 Å. The Fe(3)-O(19) bond length is 2.19 Å. The Fe(3)-O(21) bond length is 2.16 Å. The Fe(3)-O(23) bond length is 2.09 Å. The Fe(3)-O(24) bond length is 2.17 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 3-coordinate geometry to one O(14), one O(3), and one O(7) atom. The Sn(1)-O(14) bond length is 2.36 Å. The Sn(1)-O(3) bond length is 2.27 Å. The Sn(1)-O(7) bond length is 2.19 Å. In the second Sn site, Sn(2) is bonded in a 3-coordinate geometry to one O(10), one O(6), and one O(8) atom. The Sn(2)-O(10) bond length is 2.23 Å. The Sn(2)-O(6) bond length is 2.23 Å. The Sn(2)-O(8) bond length is 2.25 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(14), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-51°. The P(1)-O(10) bond length is 1.59 Å. The P(1)-O(14) bond length is 1.60 Å. The P(1)-O(16) bond length is 1.51 Å. The P(1)-O(23) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-50°. The P(2)-O(11) bond length is 1.57 Å. The P(2)-O(15) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-45°. The P(3)-O(12) bond length is 1.53 Å. The P(3)-O(17) bond length is 1.54 Å. The P(3)-O(18) bond length is 1.56 Å. The P(3)-O(4) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-46°. The P(4)-O(1) bond length is 1.57 Å. The P(4)-O(19) bond length is 1.53 Å. The P(4)-O(20) bond length is 1.55 Å. The P(4)-O(22) bond length is 1.57 Å. In the fifth P site, P(5) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-51°. The P(5)-O(24) bond length is 1.55 Å. The P(5)-O(3) bond length is 1.58 Å. The P(5)-O(5) bond length is 1.51 Å. The P(5)-O(6) bond length is 1.58 Å. In the sixth P site, P(6) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-51°. The P(6)-O(13) bond length is 1.50 Å. The P(6)-O(21) bond length is 1.55 Å. The P(6)-O(7) bond length is 1.58 Å. The P(6)-O(8) bond length is 1.59 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one Fe(2), and one P(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(4), one Fe(2), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Fe(1), one Sn(1), and one P(5) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Fe(2), and one P(3) atom to form distorted corner-sharing OLi2FeP tetrahedra. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Sn(2), and one P(5) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Sn(1), and one P(6) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Sn(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), one Sn(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Li(2), one Cr(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a linear geometry to one Cr(1) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Sn(1), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Li(2), one Fe(3), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one Li(4), one Cr(1), and one P(3) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(4), one Fe(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Fe(3), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(3), one Cr(1), and one P(4) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(1) atom. In the twenty-fourth O site, O(24) is bonded to one Li(1), one Li(4), one Fe(3), and one P(5) atom to form distorted corner-sharing OLi2FeP tetrahedra.