LiCr4(PO4)3 crystallizes in the tetragonal I-42d space group. Li(1) is bonded to four equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, and corners with four equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 78-79°. 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 corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. There are two inequivalent P sites. In the first P site, P(1) is bonded to four equivalent O(1) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra and corners with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-49°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), one Cr(1), one Cr(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLiCr2P tetrahedra.
LiCr4(PO4)3 crystallizes in the tetragonal I-42d space group. Li(1) is bonded to four equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, and corners with four equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 78-79°. All Li(1)-O(3) bond lengths are 2.27 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 corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. Both Cr(1)-O(1) bond lengths are 2.13 Å. Both Cr(1)-O(2) bond lengths are 2.23 Å. Both Cr(1)-O(3) bond lengths are 2.12 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. Both Cr(2)-O(1) bond lengths are 2.18 Å. Both Cr(2)-O(2) bond lengths are 2.28 Å. Both Cr(2)-O(3) bond lengths are 2.23 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to four equivalent O(1) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra and corners with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. All P(1)-O(1) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-49°. Both P(2)-O(2) bond lengths are 1.53 Å. Both P(2)-O(3) bond lengths are 1.59 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), one Cr(1), one Cr(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLiCr2P tetrahedra.