LiCrPO5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form LiO5 square pyramids that share corners with four equivalent P(1)O4 tetrahedra,  a cornercorner with one Cr(1)O5 trigonal bipyramid, and edges with two equivalent Cr(1)O5 trigonal bipyramids. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one Li(1)O5 square pyramid, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O5 square pyramids. 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 corners with four equivalent Li(1)O5 square pyramids and corners with four equivalent Cr(1)O5 trigonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one Cr(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped 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(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom.
LiCrPO5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form LiO5 square pyramids that share corners with four equivalent P(1)O4 tetrahedra,  a cornercorner with one Cr(1)O5 trigonal bipyramid, and edges with two equivalent Cr(1)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(2) bond length is 2.18 Å. The Li(1)-O(3) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.03 Å. The Li(1)-O(5) bond length is 2.05 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one Li(1)O5 square pyramid, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O5 square pyramids. The Cr(1)-O(1) bond length is 1.98 Å. The Cr(1)-O(2) bond length is 1.69 Å. The Cr(1)-O(3) bond length is 1.96 Å. The Cr(1)-O(4) bond length is 1.96 Å. The Cr(1)-O(5) bond length is 1.98 Å. 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 corners with four equivalent Li(1)O5 square pyramids and corners with four equivalent Cr(1)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.55 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one Cr(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped 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(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom.