Li3VCPO7 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 72-87°. In the second Li site, Li(2) 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. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-84°. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one Li(3)O5 trigonal bipyramid. 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 to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-65°. There are seven inequivalent O sites. In the first O site, O(6) is bonded to one Li(2), one Li(3), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with four equivalent O(7)Li2VP tetrahedra,  a cornercorner with one O(4)Li3P trigonal pyramid, and  an edgeedge with one O(4)Li3P trigonal pyramid. In the second O site, O(7) is bonded to one Li(2), one Li(3), one V(1), and one P(1) atom to form OLi2VP tetrahedra that share corners with three equivalent O(4)Li3P trigonal pyramids and corners with four equivalent O(6)Li2VP trigonal pyramids. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the fourth O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one C(1) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one C(1) atom. In the sixth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi3P trigonal pyramids. In the seventh O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one P(1) atom.
Li3VCPO7 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 72-87°. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(4) bond length is 2.15 Å. The Li(1)-O(5) bond length is 2.23 Å. In the second Li site, Li(2) 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 Li(2)-O(2) bond length is 2.43 Å. The Li(2)-O(3) bond length is 2.54 Å. The Li(2)-O(4) bond length is 1.98 Å. The Li(2)-O(6) bond length is 2.08 Å. The Li(2)-O(7) bond length is 2.09 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-84°. The Li(3)-O(3) bond length is 2.10 Å. The Li(3)-O(4) bond length is 2.08 Å. The Li(3)-O(5) bond length is 2.13 Å. The Li(3)-O(6) bond length is 2.10 Å. The Li(3)-O(7) bond length is 2.04 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The V(1)-O(1) bond length is 2.24 Å. The V(1)-O(2) bond length is 2.19 Å. The V(1)-O(3) bond length is 2.26 Å. The V(1)-O(5) bond length is 2.15 Å. The V(1)-O(6) bond length is 2.15 Å. The V(1)-O(7) bond length is 2.28 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 1.30 Å. The C(1)-O(2) bond length is 1.32 Å. The C(1)-O(3) bond length is 1.28 Å. P(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-65°. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.57 Å. There are seven inequivalent O sites. In the first O site, O(6) is bonded to one Li(2), one Li(3), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with four equivalent O(7)Li2VP tetrahedra,  a cornercorner with one O(4)Li3P trigonal pyramid, and  an edgeedge with one O(4)Li3P trigonal pyramid. In the second O site, O(7) is bonded to one Li(2), one Li(3), one V(1), and one P(1) atom to form OLi2VP tetrahedra that share corners with three equivalent O(4)Li3P trigonal pyramids and corners with four equivalent O(6)Li2VP trigonal pyramids. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the fourth O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one C(1) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one C(1) atom. In the sixth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi3P trigonal pyramids. In the seventh O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one P(1) atom.