Li3CrO4 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(6)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Cr(1)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 Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four 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 Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four 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 Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. In the sixth Li site, Li(6) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with four 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 Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CrO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with four 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 Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second Cr site, Cr(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CrO6 octahedra that share corners with two equivalent Li(6)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(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Cr(2) atom to form OLi5Cr octahedra that share corners with two equivalent O(3)Li5Cr octahedra, corners with four equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Cr(1) atom to form OLi5Cr octahedra that share corners with two equivalent O(4)Li5Cr octahedra, corners with four equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 6-14°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Cr(2) atom to form OLi5Cr octahedra that share corners with two equivalent O(1)Li5Cr octahedra, corners with four equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-13°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Cr(1) atom to form OLi5Cr octahedra that share corners with two equivalent O(2)Li5Cr octahedra, corners with four equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(7)Li4Cr2 octahedra, corners with four equivalent O(4)Li5Cr octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 2-17°. In the sixth O site, O(6) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(8)Li4Cr2 octahedra, corners with four equivalent O(3)Li5Cr octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-17°. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(5)Li4Cr2 octahedra, corners with four equivalent O(2)Li5Cr octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-17°. In the eighth O site, O(8) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(6)Li4Cr2 octahedra, corners with four equivalent O(1)Li5Cr octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-17°.
Li3CrO4 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(6)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(2) bond length is 2.27 Å. The Li(1)-O(3) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.03 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(8) bond length is 2.06 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. The Li(2)-O(1) bond length is 2.27 Å. The Li(2)-O(2) bond length is 2.11 Å. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(4) bond length is 2.08 Å. The Li(2)-O(5) bond length is 2.04 Å. The Li(2)-O(7) bond length is 2.06 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Cr(1)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 Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(3)-O(1) bond length is 2.07 Å. The Li(3)-O(2) bond length is 2.20 Å. The Li(3)-O(3) bond length is 1.98 Å. The Li(3)-O(4) bond length is 2.16 Å. The Li(3)-O(5) bond length is 2.27 Å. The Li(3)-O(7) bond length is 2.15 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four 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 Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(4)-O(1) bond length is 2.20 Å. The Li(4)-O(2) bond length is 2.07 Å. The Li(4)-O(3) bond length is 2.17 Å. The Li(4)-O(4) bond length is 1.98 Å. The Li(4)-O(6) bond length is 2.26 Å. The Li(4)-O(8) bond length is 2.15 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four 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 Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. The Li(5)-O(2) bond length is 2.08 Å. The Li(5)-O(4) bond length is 2.02 Å. The Li(5)-O(5) bond length is 2.08 Å. The Li(5)-O(6) bond length is 2.21 Å. The Li(5)-O(7) bond length is 2.01 Å. The Li(5)-O(8) bond length is 2.33 Å. In the sixth Li site, Li(6) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with four 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 Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-17°. The Li(6)-O(1) bond length is 2.08 Å. The Li(6)-O(3) bond length is 2.02 Å. The Li(6)-O(5) bond length is 2.21 Å. The Li(6)-O(6) bond length is 2.08 Å. The Li(6)-O(7) bond length is 2.33 Å. The Li(6)-O(8) bond length is 2.01 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CrO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with four 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 Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. The Cr(1)-O(2) bond length is 1.72 Å. The Cr(1)-O(4) bond length is 1.84 Å. The Cr(1)-O(5) bond length is 1.96 Å. The Cr(1)-O(6) bond length is 1.98 Å. The Cr(1)-O(7) bond length is 2.14 Å. The Cr(1)-O(8) bond length is 1.85 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CrO6 octahedra that share corners with two equivalent Li(6)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(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. The Cr(2)-O(1) bond length is 1.72 Å. The Cr(2)-O(3) bond length is 1.84 Å. The Cr(2)-O(5) bond length is 1.98 Å. The Cr(2)-O(6) bond length is 1.96 Å. The Cr(2)-O(7) bond length is 1.85 Å. The Cr(2)-O(8) bond length is 2.15 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Cr(2) atom to form OLi5Cr octahedra that share corners with two equivalent O(3)Li5Cr octahedra, corners with four equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Cr(1) atom to form OLi5Cr octahedra that share corners with two equivalent O(4)Li5Cr octahedra, corners with four equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 6-14°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Cr(2) atom to form OLi5Cr octahedra that share corners with two equivalent O(1)Li5Cr octahedra, corners with four equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-13°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Cr(1) atom to form OLi5Cr octahedra that share corners with two equivalent O(2)Li5Cr octahedra, corners with four equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(7)Li4Cr2 octahedra, corners with four equivalent O(4)Li5Cr octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 2-17°. In the sixth O site, O(6) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(8)Li4Cr2 octahedra, corners with four equivalent O(3)Li5Cr octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(2)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-17°. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(5)Li4Cr2 octahedra, corners with four equivalent O(2)Li5Cr octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(8)Li4Cr2 octahedra, edges with two equivalent O(1)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-17°. In the eighth O site, O(8) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Cr(1), and one Cr(2) atom to form OLi4Cr2 octahedra that share corners with two equivalent O(6)Li4Cr2 octahedra, corners with four equivalent O(1)Li5Cr octahedra, edges with two equivalent O(5)Li4Cr2 octahedra, edges with two equivalent O(6)Li4Cr2 octahedra, edges with two equivalent O(7)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with two equivalent O(3)Li5Cr octahedra, and edges with two equivalent O(4)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-17°.