LiCr(PO4)2 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(7), one O(8), and two equivalent O(3) atoms. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 12-40°. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-44°. 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 bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one Cr(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(2) atom.
LiCr(PO4)2 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(7), one O(8), and two equivalent O(3) atoms. The Li(1)-O(7) bond length is 2.35 Å. The Li(1)-O(8) bond length is 2.10 Å. There is one shorter (1.90 Å) and one longer (2.37 Å) Li(1)-O(3) bond length. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The Cr(1)-O(1) bond length is 1.94 Å. The Cr(1)-O(2) bond length is 1.92 Å. The Cr(1)-O(4) bond length is 1.98 Å. The Cr(1)-O(6) bond length is 1.60 Å. The Cr(1)-O(7) bond length is 1.94 Å. The Cr(1)-O(8) bond length is 2.07 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(4), and one O(5) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 12-40°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-44°. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.63 Å. The P(2)-O(7) bond length is 1.54 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 bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one Cr(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(2) atom.