LiCrPO5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(8), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-67°. In the second Li site, Li(2) is bonded in a distorted pentagonal planar geometry to one O(4), one O(5), one O(6), one O(7), and one O(9) atom. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(10), one O(3), one O(4), one O(6), one O(8), and one O(9) atom to form CrO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, 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 34-39°. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 34-39°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 33-54°. In the second P site, P(2) is bonded to one O(10), one O(2), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and corners with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 34-55°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(2), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one Cr(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one Cr(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom.
LiCrPO5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(8), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-67°. The Li(1)-O(1) bond length is 2.23 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(8) bond length is 2.12 Å. There is one shorter (2.17 Å) and one longer (2.18 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a distorted pentagonal planar geometry to one O(4), one O(5), one O(6), one O(7), and one O(9) atom. The Li(2)-O(4) bond length is 2.05 Å. The Li(2)-O(5) bond length is 2.33 Å. The Li(2)-O(6) bond length is 2.08 Å. The Li(2)-O(7) bond length is 2.17 Å. The Li(2)-O(9) bond length is 2.09 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(10), one O(3), one O(4), one O(6), one O(8), and one O(9) atom to form CrO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, 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 34-39°. The Cr(1)-O(10) bond length is 1.94 Å. The Cr(1)-O(3) bond length is 1.99 Å. The Cr(1)-O(4) bond length is 1.82 Å. The Cr(1)-O(6) bond length is 2.03 Å. The Cr(1)-O(8) bond length is 1.81 Å. The Cr(1)-O(9) bond length is 2.01 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 34-39°. The Cr(2)-O(1) bond length is 1.99 Å. The Cr(2)-O(2) bond length is 2.05 Å. The Cr(2)-O(4) bond length is 1.85 Å. The Cr(2)-O(5) bond length is 1.97 Å. The Cr(2)-O(7) bond length is 2.00 Å. The Cr(2)-O(8) bond length is 1.87 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(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 33-54°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(2), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and corners with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 34-55°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.55 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(2), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one Cr(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one Cr(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom.