NaLi3V4O12 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-64°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-60°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(2), one Li(3), and one V(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the sixth O site, O(6) is bonded to one Na(1), one Li(1), one Li(2), and one V(2) atom to form a mixture of distorted corner and edge-sharing ONaLi2V tetrahedra.
NaLi3V4O12 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms. Both Na(1)-O(1) bond lengths are 2.64 Å. Both Na(1)-O(4) bond lengths are 2.42 Å. Both Na(1)-O(6) bond lengths are 2.29 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.11 Å. Both Li(1)-O(5) bond lengths are 2.24 Å. Both Li(1)-O(6) bond lengths are 2.26 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Li(2)-O(2) bond lengths are 2.09 Å. Both Li(2)-O(5) bond lengths are 2.30 Å. Both Li(2)-O(6) bond lengths are 2.22 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Li(3)-O(2) bond lengths are 2.62 Å. Both Li(3)-O(3) bond lengths are 2.48 Å. Both Li(3)-O(5) bond lengths are 2.07 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-64°. The V(1)-O(1) bond length is 1.67 Å. The V(1)-O(3) bond length is 1.83 Å. The V(1)-O(4) bond length is 1.82 Å. The V(1)-O(5) bond length is 1.70 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-60°. The V(2)-O(2) bond length is 1.67 Å. The V(2)-O(3) bond length is 1.82 Å. The V(2)-O(4) bond length is 1.83 Å. The V(2)-O(6) bond length is 1.69 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(2), one Li(3), and one V(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the sixth O site, O(6) is bonded to one Na(1), one Li(1), one Li(2), and one V(2) atom to form a mixture of distorted corner and edge-sharing ONaLi2V tetrahedra.