Li3V(PO4)2 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(15), one O(5), and one O(6) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids, and corners with three equivalent Li(5)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. In the second Li site, Li(2) is bonded to one O(12), one O(16), one O(7), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(4)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids, and corners with three equivalent Li(6)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. In the third Li site, Li(3) is bonded to one O(1), one O(10), one O(5), and one O(9) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and corners with three equivalent Li(5)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. In the fourth Li site, Li(4) is bonded to one O(11), one O(12), one O(2), and one O(7) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and corners with three equivalent Li(6)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. In the fifth Li site, Li(5) is bonded to one O(1), one O(10), one O(15), and one O(5) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids, and corners with three equivalent Li(3)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 73-74°. In the sixth Li site, Li(6) is bonded to one O(12), one O(16), one O(2), and one O(7) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids, and corners with three equivalent Li(4)O4 trigonal pyramids. The corner-sharing octahedral tilt angles are 74°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(13), one O(15), one O(2), one O(4), and one O(6) atom to form VO6 octahedra that share corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  a cornercorner with one Li(6)O4 trigonal pyramid, corners with two equivalent Li(1)O4 trigonal pyramids, and corners with two equivalent Li(4)O4 trigonal pyramids. In the second V site, V(2) is bonded to one O(1), one O(14), one O(16), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  a cornercorner with one Li(6)O4 trigonal pyramid, corners with two equivalent Li(2)O4 trigonal pyramids, and corners with two equivalent Li(3)O4 trigonal pyramids. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, corners with two equivalent Li(5)O4 trigonal pyramids, and corners with three equivalent Li(3)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 34-63°. In the second P site, P(2) is bonded to one O(11), one O(2), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(6)O4 trigonal pyramids, and corners with three equivalent Li(4)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 35-64°. In the third P site, P(3) is bonded to one O(10), one O(13), one O(15), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(3)O4 trigonal pyramid, corners with two equivalent Li(5)O4 trigonal pyramids, and corners with three equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 35-64°. In the fourth P site, P(4) is bonded to one O(12), one O(14), one O(16), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra,  a cornercorner with one Li(4)O4 trigonal pyramid, corners with two equivalent Li(6)O4 trigonal pyramids, and corners with three equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 35-64°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(5), one V(2), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(10)Li3P tetrahedra, corners with three equivalent O(5)Li3P tetrahedra,  a cornercorner with one O(15)Li2VP trigonal pyramid, and  a cornercorner with one O(16)Li2VP trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), one Li(6), one V(1), and one P(2) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(12)Li3P tetrahedra, corners with three equivalent O(7)Li3P tetrahedra,  a cornercorner with one O(15)Li2VP trigonal pyramid, and  a cornercorner with one O(16)Li2VP trigonal pyramid. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(5), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(10)Li3P tetrahedra, corners with two equivalent O(15)Li2VP trigonal pyramids, and corners with three equivalent O(1)Li2VP trigonal pyramids. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded to one Li(2), one Li(4), one Li(6), and one P(2) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(12)Li3P tetrahedra, corners with two equivalent O(16)Li2VP trigonal pyramids, and corners with three equivalent O(2)Li2VP trigonal pyramids. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one P(1) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one Li(5), and one P(3) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(5)Li3P tetrahedra, corners with two equivalent O(1)Li2VP trigonal pyramids, and corners with three equivalent O(15)Li2VP trigonal pyramids. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Li(4), one V(1), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Li(2), one Li(4), one Li(6), and one P(4) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(7)Li3P tetrahedra, corners with two equivalent O(2)Li2VP trigonal pyramids, and corners with three equivalent O(16)Li2VP trigonal pyramids. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(4) atom. In the fifteenth O site, O(15) is bonded to one Li(1), one Li(5), one V(1), and one P(3) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li3P tetrahedra, corners with three equivalent O(10)Li3P tetrahedra,  a cornercorner with one O(1)Li2VP trigonal pyramid, and  a cornercorner with one O(2)Li2VP trigonal pyramid. In the sixteenth O site, O(16) is bonded to one Li(2), one Li(6), one V(2), and one P(4) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(7)Li3P tetrahedra, corners with three equivalent O(12)Li3P tetrahedra,  a cornercorner with one O(1)Li2VP trigonal pyramid, and  a cornercorner with one O(2)Li2VP trigonal pyramid.
Li3V(PO4)2 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(15), one O(5), and one O(6) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids, and corners with three equivalent Li(5)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. The Li(1)-O(10) bond length is 2.15 Å. The Li(1)-O(15) bond length is 2.18 Å. The Li(1)-O(5) bond length is 2.02 Å. The Li(1)-O(6) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(12), one O(16), one O(7), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(4)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids, and corners with three equivalent Li(6)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. The Li(2)-O(12) bond length is 2.15 Å. The Li(2)-O(16) bond length is 2.18 Å. The Li(2)-O(7) bond length is 2.02 Å. The Li(2)-O(8) bond length is 2.05 Å. In the third Li site, Li(3) is bonded to one O(1), one O(10), one O(5), and one O(9) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and corners with three equivalent Li(5)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. The Li(3)-O(1) bond length is 2.19 Å. The Li(3)-O(10) bond length is 2.03 Å. The Li(3)-O(5) bond length is 2.17 Å. The Li(3)-O(9) bond length is 2.05 Å. In the fourth Li site, Li(4) is bonded to one O(11), one O(12), one O(2), and one O(7) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and corners with three equivalent Li(6)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 63-82°. The Li(4)-O(11) bond length is 2.05 Å. The Li(4)-O(12) bond length is 2.03 Å. The Li(4)-O(2) bond length is 2.17 Å. The Li(4)-O(7) bond length is 2.16 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(10), one O(15), and one O(5) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids, and corners with three equivalent Li(3)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 73-74°. The Li(5)-O(1) bond length is 2.06 Å. The Li(5)-O(10) bond length is 2.02 Å. The Li(5)-O(15) bond length is 2.06 Å. The Li(5)-O(5) bond length is 2.02 Å. In the sixth Li site, Li(6) is bonded to one O(12), one O(16), one O(2), and one O(7) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids, and corners with three equivalent Li(4)O4 trigonal pyramids. The corner-sharing octahedral tilt angles are 74°. The Li(6)-O(12) bond length is 2.03 Å. The Li(6)-O(16) bond length is 2.06 Å. The Li(6)-O(2) bond length is 2.07 Å. The Li(6)-O(7) bond length is 2.02 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(13), one O(15), one O(2), one O(4), and one O(6) atom to form VO6 octahedra that share corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  a cornercorner with one Li(6)O4 trigonal pyramid, corners with two equivalent Li(1)O4 trigonal pyramids, and corners with two equivalent Li(4)O4 trigonal pyramids. The V(1)-O(11) bond length is 2.06 Å. The V(1)-O(13) bond length is 1.95 Å. The V(1)-O(15) bond length is 2.19 Å. The V(1)-O(2) bond length is 2.19 Å. The V(1)-O(4) bond length is 1.95 Å. The V(1)-O(6) bond length is 2.06 Å. In the second V site, V(2) is bonded to one O(1), one O(14), one O(16), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  a cornercorner with one Li(6)O4 trigonal pyramid, corners with two equivalent Li(2)O4 trigonal pyramids, and corners with two equivalent Li(3)O4 trigonal pyramids. The V(2)-O(1) bond length is 2.19 Å. The V(2)-O(14) bond length is 1.96 Å. The V(2)-O(16) bond length is 2.20 Å. The V(2)-O(3) bond length is 1.95 Å. The V(2)-O(8) bond length is 2.06 Å. The V(2)-O(9) bond length is 2.06 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, corners with two equivalent Li(5)O4 trigonal pyramids, and corners with three equivalent Li(3)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 34-63°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(11), one O(2), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(6)O4 trigonal pyramids, and corners with three equivalent Li(4)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 35-64°. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(10), one O(13), one O(15), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(3)O4 trigonal pyramid, corners with two equivalent Li(5)O4 trigonal pyramids, and corners with three equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 35-64°. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(13) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.58 Å. The P(3)-O(6) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(12), one O(14), one O(16), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra,  a cornercorner with one Li(4)O4 trigonal pyramid, corners with two equivalent Li(6)O4 trigonal pyramids, and corners with three equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 35-64°. The P(4)-O(12) bond length is 1.54 Å. The P(4)-O(14) bond length is 1.55 Å. The P(4)-O(16) bond length is 1.58 Å. The P(4)-O(8) bond length is 1.56 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(5), one V(2), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(10)Li3P tetrahedra, corners with three equivalent O(5)Li3P tetrahedra,  a cornercorner with one O(15)Li2VP trigonal pyramid, and  a cornercorner with one O(16)Li2VP trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), one Li(6), one V(1), and one P(2) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(12)Li3P tetrahedra, corners with three equivalent O(7)Li3P tetrahedra,  a cornercorner with one O(15)Li2VP trigonal pyramid, and  a cornercorner with one O(16)Li2VP trigonal pyramid. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(5), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(10)Li3P tetrahedra, corners with two equivalent O(15)Li2VP trigonal pyramids, and corners with three equivalent O(1)Li2VP trigonal pyramids. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded to one Li(2), one Li(4), one Li(6), and one P(2) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(12)Li3P tetrahedra, corners with two equivalent O(16)Li2VP trigonal pyramids, and corners with three equivalent O(2)Li2VP trigonal pyramids. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one P(1) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one Li(5), and one P(3) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(5)Li3P tetrahedra, corners with two equivalent O(1)Li2VP trigonal pyramids, and corners with three equivalent O(15)Li2VP trigonal pyramids. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Li(4), one V(1), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Li(2), one Li(4), one Li(6), and one P(4) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(7)Li3P tetrahedra, corners with two equivalent O(2)Li2VP trigonal pyramids, and corners with three equivalent O(16)Li2VP trigonal pyramids. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(4) atom. In the fifteenth O site, O(15) is bonded to one Li(1), one Li(5), one V(1), and one P(3) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li3P tetrahedra, corners with three equivalent O(10)Li3P tetrahedra,  a cornercorner with one O(1)Li2VP trigonal pyramid, and  a cornercorner with one O(2)Li2VP trigonal pyramid. In the sixteenth O site, O(16) is bonded to one Li(2), one Li(6), one V(2), and one P(4) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(7)Li3P tetrahedra, corners with three equivalent O(12)Li3P tetrahedra,  a cornercorner with one O(1)Li2VP trigonal pyramid, and  a cornercorner with one O(2)Li2VP trigonal pyramid.