LiCrPO4 crystallizes in the monoclinic P2_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), and two equivalent O(4) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one O(5), one O(6), and one O(8) atom. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a see-saw-like geometry to one O(1), one O(2), one O(5), and one O(7) atom. In the second Cr site, Cr(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(6), and two equivalent O(8) atoms. There are two 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  a cornercorner with one Li(1)O4 trigonal pyramid. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 trigonal pyramids. 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 bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Cr(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Cr(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(2) atom. In the eighth O site, O(8) is bonded to one Li(2), two equivalent Cr(2), and one P(2) atom to form distorted corner-sharing OLiCr2P tetrahedra.
LiCrPO4 crystallizes in the monoclinic P2_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), and two equivalent O(4) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(3) bond length is 1.90 Å. There is one shorter (1.96 Å) and one longer (2.29 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one O(5), one O(6), and one O(8) atom. The Li(2)-O(5) bond length is 2.06 Å. The Li(2)-O(6) bond length is 2.04 Å. The Li(2)-O(8) bond length is 2.33 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a see-saw-like geometry to one O(1), one O(2), one O(5), and one O(7) atom. The Cr(1)-O(1) bond length is 2.10 Å. The Cr(1)-O(2) bond length is 2.05 Å. The Cr(1)-O(5) bond length is 2.13 Å. The Cr(1)-O(7) bond length is 2.11 Å. In the second Cr site, Cr(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(6), and two equivalent O(8) atoms. The Cr(2)-O(3) bond length is 2.01 Å. The Cr(2)-O(4) bond length is 2.47 Å. The Cr(2)-O(6) bond length is 2.05 Å. There is one shorter (2.13 Å) and one longer (2.15 Å) Cr(2)-O(8) bond length. There are two 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  a cornercorner with one Li(1)O4 trigonal pyramid. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 trigonal pyramids. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.62 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 bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Cr(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Cr(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(2) atom. In the eighth O site, O(8) is bonded to one Li(2), two equivalent Cr(2), and one P(2) atom to form distorted corner-sharing OLiCr2P tetrahedra.