Li2Cr5(PO4)4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), one O(6), and one O(8) atom. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(7) atom to form distorted CrO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Cr(2)O5 trigonal bipyramid, and  an edgeedge with one Cr(2)O5 trigonal bipyramid. In the second Cr site, Cr(2) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted CrO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Cr(1)O5 trigonal bipyramid,  an edgeedge with one Cr(3)O6 octahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. In the third Cr site, Cr(3) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms to form distorted CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(2)O5 trigonal bipyramids. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(3)O6 octahedra, corners with two equivalent Cr(2)O5 trigonal bipyramids, and corners with three equivalent Cr(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 55°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with two equivalent Cr(1)O5 trigonal bipyramids, and corners with three equivalent Cr(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 38-45°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), one Cr(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one P(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Cr(2), one Cr(3), and one P(1) atom to form distorted corner-sharing OLiCr2P trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Cr(1), one Cr(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cr(3), and one P(2) atom.
Li2Cr5(PO4)4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), one O(6), and one O(8) atom. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.24 Å. The Li(1)-O(6) bond length is 2.41 Å. The Li(1)-O(8) bond length is 2.07 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(7) atom to form distorted CrO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Cr(2)O5 trigonal bipyramid, and  an edgeedge with one Cr(2)O5 trigonal bipyramid. The Cr(1)-O(1) bond length is 2.04 Å. The Cr(1)-O(2) bond length is 2.08 Å. The Cr(1)-O(3) bond length is 2.09 Å. The Cr(1)-O(5) bond length is 2.18 Å. The Cr(1)-O(7) bond length is 2.49 Å. In the second Cr site, Cr(2) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted CrO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Cr(1)O5 trigonal bipyramid,  an edgeedge with one Cr(3)O6 octahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. The Cr(2)-O(3) bond length is 2.10 Å. The Cr(2)-O(4) bond length is 2.22 Å. The Cr(2)-O(5) bond length is 2.09 Å. The Cr(2)-O(6) bond length is 2.09 Å. The Cr(2)-O(7) bond length is 2.12 Å. In the third Cr site, Cr(3) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms to form distorted CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(2)O5 trigonal bipyramids. Both Cr(3)-O(4) bond lengths are 2.47 Å. Both Cr(3)-O(6) bond lengths are 2.10 Å. Both Cr(3)-O(8) bond lengths are 2.08 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(3)O6 octahedra, corners with two equivalent Cr(2)O5 trigonal bipyramids, and corners with three equivalent Cr(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 55°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with two equivalent Cr(1)O5 trigonal bipyramids, and corners with three equivalent Cr(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 38-45°. The P(2)-O(3) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.54 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), one Cr(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one P(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Cr(2), one Cr(3), and one P(1) atom to form distorted corner-sharing OLiCr2P trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Cr(1), one Cr(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cr(3), and one P(2) atom.