LiCrP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(4) atoms. In the second Li site, Li(2) is bonded in a distorted hexagonal planar geometry to two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)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(5), and one O(6) 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 39-55°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-56°. There are seven 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 distorted bent 120 degrees geometry to one Li(2), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Li(1), one Cr(1), and one P(2) 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(2) 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 3-coordinate geometry to one Li(2), one Cr(1), and one P(1) 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.
LiCrP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(4) atoms. Both Li(1)-O(3) bond lengths are 2.59 Å. Both Li(1)-O(4) bond lengths are 2.36 Å. In the second Li site, Li(2) is bonded in a distorted hexagonal planar geometry to two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms. Both Li(2)-O(2) bond lengths are 2.62 Å. Both Li(2)-O(6) bond lengths are 2.51 Å. Both Li(2)-O(7) bond lengths are 2.49 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Cr(1)-O(1) bond length is 1.99 Å. The Cr(1)-O(2) bond length is 2.02 Å. The Cr(1)-O(3) bond length is 2.00 Å. The Cr(1)-O(4) bond length is 2.06 Å. The Cr(1)-O(6) bond length is 2.01 Å. The Cr(1)-O(7) bond length is 2.03 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(5), and one O(6) 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 39-55°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.63 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-56°. The P(2)-O(3) bond length is 1.52 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.61 Å. The P(2)-O(7) bond length is 1.53 Å. There are seven 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 distorted bent 120 degrees geometry to one Li(2), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Li(1), one Cr(1), and one P(2) 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(2) 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 3-coordinate geometry to one Li(2), one Cr(1), and one P(1) 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.