Li3Cr(PO3)8 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(5), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Cr(1)O6 octahedra. Cr(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-58°. In the second P site, P(2) is bonded to one O(11), one O(12), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-60°. In the third P site, P(3) is bonded to one O(1), one O(7), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-66°. In the fourth P site, P(4) is bonded to one O(2), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-63°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one P(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(2) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a linear geometry to one Li(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Li(2) and one P(2) atom.
Li3Cr(PO3)8 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. Both Li(1)-O(10) bond lengths are 2.18 Å. Both Li(1)-O(11) bond lengths are 2.14 Å. Both Li(1)-O(2) bond lengths are 2.04 Å. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(5), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Cr(1)O6 octahedra. The Li(2)-O(1) bond length is 2.29 Å. The Li(2)-O(10) bond length is 2.04 Å. The Li(2)-O(11) bond length is 2.11 Å. The Li(2)-O(12) bond length is 2.05 Å. The Li(2)-O(5) bond length is 2.32 Å. The Li(2)-O(8) bond length is 1.98 Å. Cr(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. Both Cr(1)-O(1) bond lengths are 2.05 Å. Both Cr(1)-O(4) bond lengths are 2.00 Å. Both Cr(1)-O(5) bond lengths are 2.05 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-58°. The P(1)-O(10) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.51 Å. The P(1)-O(6) bond length is 1.62 Å. The P(1)-O(7) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(11), one O(12), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-60°. The P(2)-O(11) bond length is 1.50 Å. The P(2)-O(12) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.61 Å. The P(2)-O(6) bond length is 1.61 Å. In the third P site, P(3) is bonded to one O(1), one O(7), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-66°. The P(3)-O(1) bond length is 1.52 Å. The P(3)-O(7) bond length is 1.61 Å. The P(3)-O(8) bond length is 1.48 Å. The P(3)-O(9) bond length is 1.61 Å. In the fourth P site, P(4) is bonded to one O(2), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-63°. The P(4)-O(2) bond length is 1.49 Å. The P(4)-O(3) bond length is 1.60 Å. The P(4)-O(5) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.61 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one P(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(2) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a linear geometry to one Li(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Li(2) and one P(2) atom.