Li3Cr2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-38°. In the second P site, P(2) 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 four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-49°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Cr(1) and one P(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cr(1), and one P(2) 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 rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(2) atom. In the sixth O site, O(6) 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.
Li3Cr2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), and two equivalent O(2) atoms. The Li(1)-O(3) bond length is 2.31 Å. The Li(1)-O(4) bond length is 2.14 Å. The Li(1)-O(5) bond length is 2.09 Å. The Li(1)-O(6) bond length is 2.28 Å. There is one shorter (2.13 Å) and one longer (2.58 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. Both Li(2)-O(2) bond lengths are 2.28 Å. Both Li(2)-O(4) bond lengths are 2.16 Å. Both Li(2)-O(6) bond lengths are 2.24 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. The Cr(1)-O(1) bond length is 1.92 Å. The Cr(1)-O(2) bond length is 2.01 Å. The Cr(1)-O(3) bond length is 1.98 Å. The Cr(1)-O(4) bond length is 1.99 Å. The Cr(1)-O(5) bond length is 1.99 Å. The Cr(1)-O(6) bond length is 2.03 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-38°. Both P(1)-O(3) bond lengths are 1.55 Å. Both P(1)-O(6) bond lengths are 1.56 Å. In the second P site, P(2) 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 four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-49°. The P(2)-O(1) bond length is 1.51 Å. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Cr(1) and one P(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cr(1), and one P(2) 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 rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(2) atom. In the sixth O site, O(6) 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.