Li3Cr4(PO4)6 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 5-coordinate geometry to one O(11), one O(4), one O(5), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded to two equivalent O(11), two equivalent O(12), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(4), one O(6), one O(9), and two equivalent O(1) atoms to form CrO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. In the second Cr site, Cr(2) is bonded to one O(12), one O(3), one O(5), one O(8), and two equivalent O(10) atoms to form CrO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are three 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(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and corners with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. In the second P site, P(2) is bonded to one O(12), one O(4), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-71°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, and corners with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent 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 Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Li(1), one Cr(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cr(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Cr(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(2) atom.
Li3Cr4(PO4)6 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 5-coordinate geometry to one O(11), one O(4), one O(5), one O(7), and one O(8) atom. The Li(1)-O(11) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.42 Å. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(7) bond length is 1.97 Å. The Li(1)-O(8) bond length is 2.45 Å. In the second Li site, Li(2) is bonded to two equivalent O(11), two equivalent O(12), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. Both Li(2)-O(11) bond lengths are 2.34 Å. Both Li(2)-O(12) bond lengths are 2.26 Å. Both Li(2)-O(7) bond lengths are 2.05 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(4), one O(6), one O(9), and two equivalent O(1) atoms to form CrO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The Cr(1)-O(2) bond length is 1.95 Å. The Cr(1)-O(4) bond length is 1.97 Å. The Cr(1)-O(6) bond length is 1.91 Å. The Cr(1)-O(9) bond length is 1.96 Å. There is one shorter (2.02 Å) and one longer (2.10 Å) Cr(1)-O(1) bond length. In the second Cr site, Cr(2) is bonded to one O(12), one O(3), one O(5), one O(8), and two equivalent O(10) atoms to form CrO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Cr(2)-O(12) bond length is 2.05 Å. The Cr(2)-O(3) bond length is 1.96 Å. The Cr(2)-O(5) bond length is 2.00 Å. The Cr(2)-O(8) bond length is 1.99 Å. There is one shorter (2.04 Å) and one longer (2.07 Å) Cr(2)-O(10) bond length. There are three 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(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and corners with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The P(1)-O(1) bond length is 1.60 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.50 Å. In the second P site, P(2) is bonded to one O(12), one O(4), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-71°. The P(2)-O(12) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, and corners with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. The P(3)-O(10) bond length is 1.59 Å. The P(3)-O(11) bond length is 1.51 Å. The P(3)-O(6) bond length is 1.55 Å. The P(3)-O(8) bond length is 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent 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 Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Li(1), one Cr(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cr(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Cr(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(2) atom.