Li3CrCPO7 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted pentagonal planar geometry to one O(2), one O(3), one O(5), and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(4), one O(5), and one O(6) atom. Cr(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(6) atoms to form distorted CrO5 square pyramids that share corners with four equivalent P(1)O4 tetrahedra. C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. P(1) is bonded to one O(1), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O5 square pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one C(1) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one Cr(1), and one P(1) atom to form OLi2CrP tetrahedra that share corners with six equivalent O(6)Li2CrP trigonal pyramids and  an edgeedge with one O(5)Li3C trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one C(1) atom to form distorted edge-sharing OLi3C trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Cr(1), and one P(1) atom to form distorted OLi2CrP trigonal pyramids that share corners with three equivalent O(4)Li2CrP tetrahedra,  a cornercorner with one O(6)Li2CrP trigonal pyramid,  an edgeedge with one O(6)Li2CrP trigonal pyramid, and  an edgeedge with one O(5)Li3C trigonal pyramid.
Li3CrCPO7 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted pentagonal planar geometry to one O(2), one O(3), one O(5), and two equivalent O(6) atoms. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(5) bond length is 2.32 Å. Both Li(1)-O(6) bond lengths are 2.37 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(4), one O(5), and one O(6) atom. The Li(2)-O(1) bond length is 2.10 Å. The Li(2)-O(4) bond length is 2.13 Å. The Li(2)-O(5) bond length is 1.96 Å. The Li(2)-O(6) bond length is 2.18 Å. Cr(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(6) atoms to form distorted CrO5 square pyramids that share corners with four equivalent P(1)O4 tetrahedra. The Cr(1)-O(1) bond length is 2.48 Å. The Cr(1)-O(2) bond length is 2.05 Å. The Cr(1)-O(4) bond length is 2.09 Å. Both Cr(1)-O(6) bond lengths are 2.05 Å. C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. The C(1)-O(2) bond length is 1.32 Å. The C(1)-O(3) bond length is 1.28 Å. The C(1)-O(5) bond length is 1.30 Å. P(1) is bonded to one O(1), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O5 square pyramids. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.57 Å. Both P(1)-O(6) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one C(1) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one Cr(1), and one P(1) atom to form OLi2CrP tetrahedra that share corners with six equivalent O(6)Li2CrP trigonal pyramids and  an edgeedge with one O(5)Li3C trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one C(1) atom to form distorted edge-sharing OLi3C trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Cr(1), and one P(1) atom to form distorted OLi2CrP trigonal pyramids that share corners with three equivalent O(4)Li2CrP tetrahedra,  a cornercorner with one O(6)Li2CrP trigonal pyramid,  an edgeedge with one O(6)Li2CrP trigonal pyramid, and  an edgeedge with one O(5)Li3C trigonal pyramid.