Li2CrP2O7 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(2), one O(5), one O(6), and one O(7) atom. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(6), and one O(7) atom to form distorted CrO5 square pyramids 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(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O5 square pyramids and  a cornercorner with one P(2)O4 tetrahedra. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O5 square pyramids and  a cornercorner with one P(1)O4 tetrahedra. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted 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 distorted rectangular see-saw-like geometry to one Li(1), one Li(2), 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(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(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(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(2) atom.
Li2CrP2O7 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(1)-O(1) bond length is 1.92 Å. The Li(1)-O(2) bond length is 2.14 Å. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-O(5) bond length is 1.97 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(2), one O(5), one O(6), and one O(7) atom. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(5) bond length is 1.92 Å. The Li(2)-O(6) bond length is 1.96 Å. The Li(2)-O(7) bond length is 1.97 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(6), and one O(7) atom to form distorted CrO5 square pyramids 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 2.49 Å. The Cr(1)-O(2) bond length is 2.12 Å. The Cr(1)-O(3) bond length is 2.09 Å. The Cr(1)-O(6) bond length is 2.04 Å. The Cr(1)-O(7) bond length is 2.08 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(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O5 square pyramids and  a cornercorner with one P(2)O4 tetrahedra. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O5 square pyramids and  a cornercorner with one P(1)O4 tetrahedra. The P(2)-O(4) bond length is 1.62 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.54 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted 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 distorted rectangular see-saw-like geometry to one Li(1), one Li(2), 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(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(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(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(2) atom.