Li3Cr2Mn2O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) 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 six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Cr(1), one Mn(1), and one Mn(2) atom to form OLi2Mn2Cr square pyramids that share corners with two equivalent O(2)Li2MnCr2 square pyramids, corners with two equivalent O(3)Li2MnCr2 square pyramids, corners with five equivalent O(1)Li2Mn2Cr square pyramids, edges with four equivalent O(4)Li3Mn2Cr octahedra, edges with two equivalent O(2)Li2MnCr2 square pyramids, and edges with two equivalent O(3)Li2MnCr2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Cr(1), one Cr(2), and one Mn(2) atom to form OLi2MnCr2 square pyramids that share corners with two equivalent O(1)Li2Mn2Cr square pyramids, corners with two equivalent O(3)Li2MnCr2 square pyramids, corners with five equivalent O(2)Li2MnCr2 square pyramids, edges with four equivalent O(4)Li3Mn2Cr octahedra, edges with two equivalent O(1)Li2Mn2Cr square pyramids, and edges with two equivalent O(3)Li2MnCr2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cr(1), one Cr(2), and one Mn(1) atom to form OLi2MnCr2 square pyramids that share corners with two equivalent O(1)Li2Mn2Cr square pyramids, corners with two equivalent O(2)Li2MnCr2 square pyramids, corners with five equivalent O(3)Li2MnCr2 square pyramids, edges with four equivalent O(4)Li3Mn2Cr octahedra, edges with two equivalent O(1)Li2Mn2Cr square pyramids, and edges with two equivalent O(2)Li2MnCr2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Cr(2), one Mn(1), and one Mn(2) atom to form OLi3Mn2Cr octahedra that share corners with six equivalent O(4)Li3Mn2Cr octahedra, edges with four equivalent O(1)Li2Mn2Cr square pyramids, edges with four equivalent O(2)Li2MnCr2 square pyramids, and edges with four equivalent O(3)Li2MnCr2 square pyramids. The corner-sharing octahedra are not tilted.
Li3Cr2Mn2O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) 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 six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Li(1)-O(1) bond lengths are 2.32 Å. Both Li(1)-O(2) bond lengths are 2.19 Å. Both Li(1)-O(4) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Li(2)-O(1) bond lengths are 2.18 Å. Both Li(2)-O(3) bond lengths are 2.20 Å. Both Li(2)-O(4) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. Both Li(3)-O(2) bond lengths are 2.15 Å. Both Li(3)-O(3) bond lengths are 2.26 Å. Both Li(3)-O(4) bond lengths are 2.13 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. Both Cr(1)-O(1) bond lengths are 2.00 Å. Both Cr(1)-O(2) bond lengths are 2.01 Å. Both Cr(1)-O(3) bond lengths are 2.00 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. Both Cr(2)-O(2) bond lengths are 2.04 Å. Both Cr(2)-O(3) bond lengths are 2.04 Å. Both Cr(2)-O(4) bond lengths are 2.02 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Mn(1)-O(1) bond lengths are 2.01 Å. Both Mn(1)-O(3) bond lengths are 1.95 Å. Both Mn(1)-O(4) bond lengths are 2.22 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Mn(2)-O(1) bond lengths are 1.98 Å. Both Mn(2)-O(2) bond lengths are 1.96 Å. Both Mn(2)-O(4) bond lengths are 1.96 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Cr(1), one Mn(1), and one Mn(2) atom to form OLi2Mn2Cr square pyramids that share corners with two equivalent O(2)Li2MnCr2 square pyramids, corners with two equivalent O(3)Li2MnCr2 square pyramids, corners with five equivalent O(1)Li2Mn2Cr square pyramids, edges with four equivalent O(4)Li3Mn2Cr octahedra, edges with two equivalent O(2)Li2MnCr2 square pyramids, and edges with two equivalent O(3)Li2MnCr2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Cr(1), one Cr(2), and one Mn(2) atom to form OLi2MnCr2 square pyramids that share corners with two equivalent O(1)Li2Mn2Cr square pyramids, corners with two equivalent O(3)Li2MnCr2 square pyramids, corners with five equivalent O(2)Li2MnCr2 square pyramids, edges with four equivalent O(4)Li3Mn2Cr octahedra, edges with two equivalent O(1)Li2Mn2Cr square pyramids, and edges with two equivalent O(3)Li2MnCr2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cr(1), one Cr(2), and one Mn(1) atom to form OLi2MnCr2 square pyramids that share corners with two equivalent O(1)Li2Mn2Cr square pyramids, corners with two equivalent O(2)Li2MnCr2 square pyramids, corners with five equivalent O(3)Li2MnCr2 square pyramids, edges with four equivalent O(4)Li3Mn2Cr octahedra, edges with two equivalent O(1)Li2Mn2Cr square pyramids, and edges with two equivalent O(2)Li2MnCr2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Cr(2), one Mn(1), and one Mn(2) atom to form OLi3Mn2Cr octahedra that share corners with six equivalent O(4)Li3Mn2Cr octahedra, edges with four equivalent O(1)Li2Mn2Cr square pyramids, edges with four equivalent O(2)Li2MnCr2 square pyramids, and edges with four equivalent O(3)Li2MnCr2 square pyramids. The corner-sharing octahedra are not tilted.