LiV4(PO4)3 crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded in a distorted water-like geometry to two equivalent O(4) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one O(7), one O(9), and two equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-47°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO5 square pyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent V(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 63-78°. In the third V site, V(3) is bonded to one O(2), one O(5), one O(6), one O(9), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-47°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(6), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 36°. In the second P site, P(2) is bonded to one O(5), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O5 square pyramids, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-63°. In the third P site, P(3) is bonded to one O(3), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 36°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded to one V(3), two equivalent V(2), and one P(1) atom to form a mixture of distorted edge and corner-sharing OV3P tetrahedra. In the third O site, O(3) is bonded to one V(1), two equivalent V(2), and one P(3) atom to form a mixture of distorted edge and corner-sharing OV3P trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded to one V(3), two equivalent V(2), and one P(1) atom to form a mixture of distorted edge and corner-sharing OV3P trigonal pyramids. In the seventh O site, O(7) is bonded to one V(1), two equivalent V(2), and one P(3) atom to form a mixture of distorted edge and corner-sharing OV3P tetrahedra. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom.
LiV4(PO4)3 crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded in a distorted water-like geometry to two equivalent O(4) atoms. Both Li(1)-O(4) bond lengths are 2.47 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one O(7), one O(9), and two equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-47°. The V(1)-O(3) bond length is 2.37 Å. The V(1)-O(5) bond length is 2.09 Å. The V(1)-O(7) bond length is 2.22 Å. The V(1)-O(9) bond length is 2.12 Å. Both V(1)-O(1) bond lengths are 2.12 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO5 square pyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent V(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 63-78°. The V(2)-O(2) bond length is 2.19 Å. The V(2)-O(3) bond length is 2.21 Å. The V(2)-O(4) bond length is 2.09 Å. The V(2)-O(6) bond length is 2.22 Å. The V(2)-O(7) bond length is 2.19 Å. In the third V site, V(3) is bonded to one O(2), one O(5), one O(6), one O(9), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-47°. The V(3)-O(2) bond length is 2.22 Å. The V(3)-O(5) bond length is 2.13 Å. The V(3)-O(6) bond length is 2.32 Å. The V(3)-O(9) bond length is 2.18 Å. Both V(3)-O(8) bond lengths are 2.11 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(6), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 36°. The P(1)-O(2) bond length is 1.61 Å. The P(1)-O(6) bond length is 1.60 Å. Both P(1)-O(1) bond lengths are 1.52 Å. In the second P site, P(2) is bonded to one O(5), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O5 square pyramids, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-63°. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.57 Å. Both P(2)-O(4) bond lengths are 1.56 Å. In the third P site, P(3) is bonded to one O(3), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O5 square pyramids, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 36°. The P(3)-O(3) bond length is 1.60 Å. The P(3)-O(7) bond length is 1.61 Å. Both P(3)-O(8) bond lengths are 1.52 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded to one V(3), two equivalent V(2), and one P(1) atom to form a mixture of distorted edge and corner-sharing OV3P tetrahedra. In the third O site, O(3) is bonded to one V(1), two equivalent V(2), and one P(3) atom to form a mixture of distorted edge and corner-sharing OV3P trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded to one V(3), two equivalent V(2), and one P(1) atom to form a mixture of distorted edge and corner-sharing OV3P trigonal pyramids. In the seventh O site, O(7) is bonded to one V(1), two equivalent V(2), and one P(3) atom to form a mixture of distorted edge and corner-sharing OV3P tetrahedra. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom.