Li3Cr2P5O16 crystallizes in the monoclinic P2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-73°. In the second Li site, Li(2) is bonded in a see-saw-like geometry to two equivalent O(5) and two equivalent O(7) atoms. Cr(1) 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 CrO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-62°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-57°. In the third P site, P(3) is bonded to two equivalent O(7) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Cr(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom.
Li3Cr2P5O16 crystallizes in the monoclinic P2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-73°. The Li(1)-O(1) bond length is 2.09 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.25 Å. In the second Li site, Li(2) is bonded in a see-saw-like geometry to two equivalent O(5) and two equivalent O(7) atoms. Both Li(2)-O(5) bond lengths are 2.12 Å. Both Li(2)-O(7) bond lengths are 2.05 Å. Cr(1) 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 CrO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. The Cr(1)-O(1) bond length is 2.05 Å. The Cr(1)-O(2) bond length is 2.11 Å. The Cr(1)-O(3) bond length is 2.48 Å. The Cr(1)-O(4) bond length is 2.17 Å. The Cr(1)-O(5) bond length is 2.41 Å. The Cr(1)-O(7) bond length is 2.06 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-62°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(6) bond length is 1.65 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-57°. The P(2)-O(3) bond length is 1.50 Å. The P(2)-O(4) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.61 Å. In the third P site, P(3) is bonded to two equivalent O(7) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. Both P(3)-O(7) bond lengths are 1.51 Å. Both P(3)-O(8) bond lengths are 1.59 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Cr(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom.