LiCr4(PO4)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded in an L-shaped geometry to two equivalent O(12) atoms. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(3), one O(9), and two equivalent O(8) atoms to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cr(1)O5 trigonal bipyramid, and  an edgeedge with one Cr(4)O5 trigonal bipyramid. In the second Cr site, Cr(2) is bonded to one O(1), one O(5), one O(6), and two equivalent O(10) atoms to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Cr(2)O5 trigonal bipyramid. In the third Cr site, Cr(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(5), one O(9), and two equivalent O(4) atoms. In the fourth Cr site, Cr(4) is bonded to one O(11), one O(12), one O(3), one O(7), and one O(9) atom to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O5 trigonal bipyramid, corners with two equivalent Cr(2)O5 trigonal bipyramids, and corners with two equivalent Cr(4)O5 trigonal bipyramids. In the second P site, P(2) 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 Cr(2)O5 trigonal bipyramid, corners with two equivalent Cr(1)O5 trigonal bipyramids, and corners with two equivalent Cr(4)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(10), one O(12), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(4)O5 trigonal bipyramid, corners with two equivalent Cr(1)O5 trigonal bipyramids, and corners with two equivalent Cr(2)O5 trigonal bipyramids. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cr(2), one Cr(3), and one P(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cr(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(4), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Cr(3) and one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Cr(2), one Cr(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cr(4) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Cr(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Cr(1), one Cr(3), one Cr(4), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to two equivalent Cr(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Cr(3), one Cr(4), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Cr(4), and one P(3) atom.
LiCr4(PO4)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded in an L-shaped geometry to two equivalent O(12) atoms. There is one shorter (1.99 Å) and one longer (2.01 Å) Li(1)-O(12) bond length. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(3), one O(9), and two equivalent O(8) atoms to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cr(1)O5 trigonal bipyramid, and  an edgeedge with one Cr(4)O5 trigonal bipyramid. The Cr(1)-O(2) bond length is 2.07 Å. The Cr(1)-O(3) bond length is 2.09 Å. The Cr(1)-O(9) bond length is 2.46 Å. There is one shorter (2.06 Å) and one longer (2.13 Å) Cr(1)-O(8) bond length. In the second Cr site, Cr(2) is bonded to one O(1), one O(5), one O(6), and two equivalent O(10) atoms to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Cr(2)O5 trigonal bipyramid. The Cr(2)-O(1) bond length is 2.10 Å. The Cr(2)-O(5) bond length is 2.11 Å. The Cr(2)-O(6) bond length is 2.01 Å. There is one shorter (2.04 Å) and one longer (2.57 Å) Cr(2)-O(10) bond length. In the third Cr site, Cr(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(5), one O(9), and two equivalent O(4) atoms. The Cr(3)-O(1) bond length is 2.06 Å. The Cr(3)-O(11) bond length is 2.05 Å. The Cr(3)-O(5) bond length is 2.11 Å. The Cr(3)-O(9) bond length is 2.68 Å. There is one shorter (2.05 Å) and one longer (2.51 Å) Cr(3)-O(4) bond length. In the fourth Cr site, Cr(4) is bonded to one O(11), one O(12), one O(3), one O(7), and one O(9) atom to form distorted CrO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Cr(1)O5 trigonal bipyramid. The Cr(4)-O(11) bond length is 2.05 Å. The Cr(4)-O(12) bond length is 2.57 Å. The Cr(4)-O(3) bond length is 2.14 Å. The Cr(4)-O(7) bond length is 2.02 Å. The Cr(4)-O(9) bond length is 2.07 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O5 trigonal bipyramid, corners with two equivalent Cr(2)O5 trigonal bipyramids, and corners with two equivalent Cr(4)O5 trigonal bipyramids. The P(1)-O(11) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.51 Å. The P(1)-O(9) bond length is 1.57 Å. In the second P site, P(2) 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 Cr(2)O5 trigonal bipyramid, corners with two equivalent Cr(1)O5 trigonal bipyramids, and corners with two equivalent Cr(4)O5 trigonal bipyramids. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(3) bond length is 1.59 Å. The P(2)-O(7) bond length is 1.53 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(4)O5 trigonal bipyramid, corners with two equivalent Cr(1)O5 trigonal bipyramids, and corners with two equivalent Cr(2)O5 trigonal bipyramids. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(4) bond length is 1.55 Å. The P(3)-O(8) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cr(2), one Cr(3), and one P(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cr(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(4), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Cr(3) and one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Cr(2), one Cr(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cr(4) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Cr(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Cr(1), one Cr(3), one Cr(4), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to two equivalent Cr(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Cr(3), one Cr(4), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Cr(4), and one P(3) atom.