Li3CrBPO7 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 4-coordinate geometry to one O(1), one O(2), and two equivalent O(4) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. Cr(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. P(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-51°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), and one B(1) atom to form OLi3B tetrahedra that share corners with three equivalent O(3)Li2CrB tetrahedra and corners with four equivalent O(4)Li2CrP trigonal pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Li(2), one Cr(1), and one B(1) atom. In the third O site, O(3) is bonded to two equivalent Li(2), one Cr(1), and one B(1) atom to form distorted OLi2CrB tetrahedra that share corners with three equivalent O(1)Li3B tetrahedra and corners with four equivalent O(4)Li2CrP trigonal pyramids. In the fourth O site, O(4) 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 two equivalent O(3)Li2CrB tetrahedra, corners with two equivalent O(1)Li3B tetrahedra,  a cornercorner with one O(4)Li2CrP trigonal pyramid, and  an edgeedge with one O(4)Li2CrP trigonal pyramid. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one Cr(1), and one P(1) atom.
Li3CrBPO7 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 4-coordinate geometry to one O(1), one O(2), and two equivalent O(4) atoms. The Li(1)-O(1) bond length is 2.03 Å. The Li(1)-O(2) bond length is 2.00 Å. Both Li(1)-O(4) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The Li(2)-O(1) bond length is 1.98 Å. The Li(2)-O(2) bond length is 2.52 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-O(4) bond length is 2.25 Å. The Li(2)-O(6) bond length is 2.25 Å. Cr(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. The Cr(1)-O(2) bond length is 2.05 Å. The Cr(1)-O(3) bond length is 1.97 Å. The Cr(1)-O(5) bond length is 2.02 Å. The Cr(1)-O(6) bond length is 2.02 Å. Both Cr(1)-O(4) bond lengths are 2.01 Å. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.35 Å. The B(1)-O(2) bond length is 1.41 Å. The B(1)-O(3) bond length is 1.41 Å. P(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-51°. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.54 Å. Both P(1)-O(4) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), and one B(1) atom to form OLi3B tetrahedra that share corners with three equivalent O(3)Li2CrB tetrahedra and corners with four equivalent O(4)Li2CrP trigonal pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Li(2), one Cr(1), and one B(1) atom. In the third O site, O(3) is bonded to two equivalent Li(2), one Cr(1), and one B(1) atom to form distorted OLi2CrB tetrahedra that share corners with three equivalent O(1)Li3B tetrahedra and corners with four equivalent O(4)Li2CrP trigonal pyramids. In the fourth O site, O(4) 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 two equivalent O(3)Li2CrB tetrahedra, corners with two equivalent O(1)Li3B tetrahedra,  a cornercorner with one O(4)Li2CrP trigonal pyramid, and  an edgeedge with one O(4)Li2CrP trigonal pyramid. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one Cr(1), and one P(1) atom.