Li3CrCPO7 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one O(5) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(5), one O(6), and one O(7) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(5), one O(6), and one O(7) atom. Cr(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(6), and one O(7) atom. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. P(1) is bonded in a tetrahedral geometry to one O(4), one O(5), one O(6), and one O(7) atom. There are seven inequivalent O sites. In the first O site, O(6) is bonded to one Li(2), one Li(3), one Cr(1), and one P(1) atom to form distorted OLi2CrP trigonal pyramids that share corners with two equivalent O(2)Li2CrC tetrahedra, corners with four equivalent O(7)Li2CrP tetrahedra,  a cornercorner with one O(5)Li3P trigonal pyramid, and  an edgeedge with one O(5)Li3P trigonal pyramid. In the second O site, O(7) is bonded to one Li(2), one Li(3), one Cr(1), and one P(1) atom to form distorted OLi2CrP tetrahedra that share corners with three equivalent O(5)Li3P trigonal pyramids, corners with four equivalent O(6)Li2CrP trigonal pyramids, and  an edgeedge with one O(2)Li2CrC tetrahedra. In the third O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one C(1) atom. In the fourth O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), and one C(1) atom to form distorted OLi2CrC tetrahedra that share corners with two equivalent O(6)Li2CrP trigonal pyramids, corners with two equivalent O(5)Li3P trigonal pyramids, and  an edgeedge with one O(7)Li2CrP tetrahedra. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Cr(1), and one C(1) atom. In the sixth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Cr(1), and one P(1) atom. In the seventh O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form distorted OLi3P trigonal pyramids that share corners with two equivalent O(2)Li2CrC tetrahedra, corners with three equivalent O(7)Li2CrP tetrahedra,  a cornercorner with one O(6)Li2CrP trigonal pyramid, and  an edgeedge with one O(6)Li2CrP trigonal pyramid.
Li3CrCPO7 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one O(5) atom. The Li(1)-O(1) bond length is 1.92 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.23 Å. The Li(1)-O(5) bond length is 2.13 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(5), one O(6), and one O(7) atom. The Li(2)-O(2) bond length is 2.34 Å. The Li(2)-O(3) bond length is 2.58 Å. The Li(2)-O(5) bond length is 2.03 Å. The Li(2)-O(6) bond length is 2.06 Å. The Li(2)-O(7) bond length is 2.06 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Li(3)-O(3) bond length is 2.26 Å. The Li(3)-O(4) bond length is 2.09 Å. The Li(3)-O(5) bond length is 2.03 Å. The Li(3)-O(6) bond length is 2.13 Å. The Li(3)-O(7) bond length is 2.01 Å. Cr(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(6), and one O(7) atom. The Cr(1)-O(2) bond length is 2.10 Å. The Cr(1)-O(3) bond length is 2.11 Å. The Cr(1)-O(4) bond length is 2.11 Å. The Cr(1)-O(6) bond length is 2.07 Å. The Cr(1)-O(7) bond length is 2.47 Å. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The C(1)-O(1) bond length is 1.28 Å. The C(1)-O(2) bond length is 1.33 Å. The C(1)-O(3) bond length is 1.29 Å. P(1) is bonded in a tetrahedral geometry to one O(4), one O(5), one O(6), and one O(7) atom. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.55 Å. There are seven inequivalent O sites. In the first O site, O(6) is bonded to one Li(2), one Li(3), one Cr(1), and one P(1) atom to form distorted OLi2CrP trigonal pyramids that share corners with two equivalent O(2)Li2CrC tetrahedra, corners with four equivalent O(7)Li2CrP tetrahedra,  a cornercorner with one O(5)Li3P trigonal pyramid, and  an edgeedge with one O(5)Li3P trigonal pyramid. In the second O site, O(7) is bonded to one Li(2), one Li(3), one Cr(1), and one P(1) atom to form distorted OLi2CrP tetrahedra that share corners with three equivalent O(5)Li3P trigonal pyramids, corners with four equivalent O(6)Li2CrP trigonal pyramids, and  an edgeedge with one O(2)Li2CrC tetrahedra. In the third O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one C(1) atom. In the fourth O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), and one C(1) atom to form distorted OLi2CrC tetrahedra that share corners with two equivalent O(6)Li2CrP trigonal pyramids, corners with two equivalent O(5)Li3P trigonal pyramids, and  an edgeedge with one O(7)Li2CrP tetrahedra. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Cr(1), and one C(1) atom. In the sixth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Cr(1), and one P(1) atom. In the seventh O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form distorted OLi3P trigonal pyramids that share corners with two equivalent O(2)Li2CrC tetrahedra, corners with three equivalent O(7)Li2CrP tetrahedra,  a cornercorner with one O(6)Li2CrP trigonal pyramid, and  an edgeedge with one O(6)Li2CrP trigonal pyramid.