Li3Cr(PO4)2 crystallizes in the trigonal R3 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(8), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(1) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(6) atoms. In the fourth Li site, Li(4) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Cr(2)O6 octahedra. In the fifth Li site, Li(5) is bonded to three equivalent O(5) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Cr(1)O6 octahedra, and  a faceface with one Cr(3)O6 octahedra. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to three equivalent O(5) and three equivalent O(7) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. In the second Cr site, Cr(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(4)O6 octahedra. In the third Cr site, Cr(3) is bonded to three equivalent O(3) and three equivalent O(8) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. In the second P site, P(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(2) atom. In the second O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the third O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(5), one Cr(3), and one P(2) atom. In the fourth O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), two equivalent Li(2), and one P(1) atom. In the fifth O site, O(2) is bonded in a 5-coordinate geometry to one Li(4), two equivalent Li(1), one Cr(2), and one P(2) atom. In the sixth O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(3), and one P(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cr(2), and one P(1) atom. In the eighth O site, O(5) is bonded to one Li(2), one Li(5), one Cr(1), and one P(1) atom to form distorted edge-sharing OLi2CrP trigonal pyramids.
Li3Cr(PO4)2 crystallizes in the trigonal R3 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(8), and two equivalent O(2) atoms. The Li(1)-O(3) bond length is 2.36 Å. The Li(1)-O(4) bond length is 2.26 Å. The Li(1)-O(8) bond length is 2.07 Å. There is one shorter (2.11 Å) and one longer (2.54 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(1) atoms. The Li(2)-O(5) bond length is 2.30 Å. The Li(2)-O(6) bond length is 1.95 Å. There is one shorter (2.02 Å) and one longer (2.21 Å) Li(2)-O(1) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(6) atoms. All Li(3)-O(1) bond lengths are 2.26 Å. All Li(3)-O(6) bond lengths are 1.97 Å. In the fourth Li site, Li(4) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Cr(2)O6 octahedra. All Li(4)-O(1) bond lengths are 2.08 Å. All Li(4)-O(2) bond lengths are 2.32 Å. In the fifth Li site, Li(5) is bonded to three equivalent O(5) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Cr(1)O6 octahedra, and  a faceface with one Cr(3)O6 octahedra. All Li(5)-O(5) bond lengths are 2.18 Å. All Li(5)-O(8) bond lengths are 2.25 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to three equivalent O(5) and three equivalent O(7) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. All Cr(1)-O(5) bond lengths are 2.04 Å. All Cr(1)-O(7) bond lengths are 2.00 Å. In the second Cr site, Cr(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(4)O6 octahedra. All Cr(2)-O(2) bond lengths are 2.03 Å. All Cr(2)-O(4) bond lengths are 1.99 Å. In the third Cr site, Cr(3) is bonded to three equivalent O(3) and three equivalent O(8) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. All Cr(3)-O(3) bond lengths are 1.96 Å. All Cr(3)-O(8) bond lengths are 2.02 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.58 Å. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(2) atom. In the second O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the third O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(5), one Cr(3), and one P(2) atom. In the fourth O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), two equivalent Li(2), and one P(1) atom. In the fifth O site, O(2) is bonded in a 5-coordinate geometry to one Li(4), two equivalent Li(1), one Cr(2), and one P(2) atom. In the sixth O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(3), and one P(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cr(2), and one P(1) atom. In the eighth O site, O(5) is bonded to one Li(2), one Li(5), one Cr(1), and one P(1) atom to form distorted edge-sharing OLi2CrP trigonal pyramids.