Li3VCPO7 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(2), one O(5), and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form LiO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-88°. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra, corners with four equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. P(1) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and corners with six equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-62°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one V(1), and one C(1) atom to form distorted OLi2VC trigonal pyramids that share corners with three equivalent O(4)Li2VP tetrahedra, corners with three equivalent O(5)Li3C tetrahedra,  a cornercorner with one O(3)Li2VP trigonal pyramid, corners with four equivalent O(6)Li2VP trigonal pyramids, and  an edgeedge with one O(3)Li2VP trigonal pyramid. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(1) atom. In the third O site, O(3) is bonded to two equivalent Li(2), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li3C tetrahedra, corners with four equivalent O(4)Li2VP tetrahedra,  a cornercorner with one O(1)Li2VC trigonal pyramid, corners with two equivalent O(6)Li2VP trigonal pyramids,  an edgeedge with one O(1)Li2VC trigonal pyramid, and edges with two equivalent O(6)Li2VP trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), and one P(1) atom to form distorted OLi2VP tetrahedra that share corners with three equivalent O(1)Li2VC trigonal pyramids, corners with four equivalent O(3)Li2VP trigonal pyramids, corners with six equivalent O(6)Li2VP trigonal pyramids, and  an edgeedge with one O(5)Li3C tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one C(1) atom to form OLi3C tetrahedra that share corners with two equivalent O(3)Li2VP trigonal pyramids, corners with three equivalent O(1)Li2VC trigonal pyramids, corners with four equivalent O(6)Li2VP trigonal pyramids, and  an edgeedge with one O(4)Li2VP tetrahedra. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li3C tetrahedra, corners with three equivalent O(4)Li2VP tetrahedra,  a cornercorner with one O(3)Li2VP trigonal pyramid,  a cornercorner with one O(6)Li2VP trigonal pyramid, corners with two equivalent O(1)Li2VC trigonal pyramids,  an edgeedge with one O(3)Li2VP trigonal pyramid, and  an edgeedge with one O(6)Li2VP trigonal pyramid.
Li3VCPO7 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(2), one O(5), and two equivalent O(6) atoms. The Li(1)-O(2) bond length is 1.92 Å. The Li(1)-O(5) bond length is 2.01 Å. Both Li(1)-O(6) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form LiO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-88°. The Li(2)-O(1) bond length is 2.29 Å. The Li(2)-O(3) bond length is 2.21 Å. The Li(2)-O(4) bond length is 2.18 Å. The Li(2)-O(5) bond length is 2.15 Å. The Li(2)-O(6) bond length is 2.15 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra, corners with four equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The V(1)-O(1) bond length is 2.21 Å. The V(1)-O(2) bond length is 2.23 Å. The V(1)-O(3) bond length is 2.16 Å. The V(1)-O(4) bond length is 2.20 Å. Both V(1)-O(6) bond lengths are 2.11 Å. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. The C(1)-O(1) bond length is 1.31 Å. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(5) bond length is 1.29 Å. P(1) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and corners with six equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-62°. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.56 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 to two equivalent Li(2), one V(1), and one C(1) atom to form distorted OLi2VC trigonal pyramids that share corners with three equivalent O(4)Li2VP tetrahedra, corners with three equivalent O(5)Li3C tetrahedra,  a cornercorner with one O(3)Li2VP trigonal pyramid, corners with four equivalent O(6)Li2VP trigonal pyramids, and  an edgeedge with one O(3)Li2VP trigonal pyramid. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(1) atom. In the third O site, O(3) is bonded to two equivalent Li(2), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li3C tetrahedra, corners with four equivalent O(4)Li2VP tetrahedra,  a cornercorner with one O(1)Li2VC trigonal pyramid, corners with two equivalent O(6)Li2VP trigonal pyramids,  an edgeedge with one O(1)Li2VC trigonal pyramid, and edges with two equivalent O(6)Li2VP trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), and one P(1) atom to form distorted OLi2VP tetrahedra that share corners with three equivalent O(1)Li2VC trigonal pyramids, corners with four equivalent O(3)Li2VP trigonal pyramids, corners with six equivalent O(6)Li2VP trigonal pyramids, and  an edgeedge with one O(5)Li3C tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one C(1) atom to form OLi3C tetrahedra that share corners with two equivalent O(3)Li2VP trigonal pyramids, corners with three equivalent O(1)Li2VC trigonal pyramids, corners with four equivalent O(6)Li2VP trigonal pyramids, and  an edgeedge with one O(4)Li2VP tetrahedra. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li3C tetrahedra, corners with three equivalent O(4)Li2VP tetrahedra,  a cornercorner with one O(3)Li2VP trigonal pyramid,  a cornercorner with one O(6)Li2VP trigonal pyramid, corners with two equivalent O(1)Li2VC trigonal pyramids,  an edgeedge with one O(3)Li2VP trigonal pyramid, and  an edgeedge with one O(6)Li2VP trigonal pyramid.