NaLiV(OF)2 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent F(1), and three equivalent F(2) atoms. Li(1) is bonded to three equivalent O(2) and one F(2) atom to form distorted LiO3F trigonal pyramids that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids,  an edgeedge with one V(1)O4F2 octahedra, and edges with two equivalent Li(1)O3F trigonal pyramids. The corner-sharing octahedral tilt angles are 75°. V(1) is bonded to one O(2), three equivalent O(1), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, edges with two equivalent V(1)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles are 22°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), three equivalent Li(1), and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Li(1), and one V(1) atom.
NaLiV(OF)2 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent F(1), and three equivalent F(2) atoms. The Na(1)-O(2) bond length is 2.40 Å. Both Na(1)-F(1) bond lengths are 2.24 Å. There is one shorter (2.26 Å) and two longer (2.56 Å) Na(1)-F(2) bond lengths. Li(1) is bonded to three equivalent O(2) and one F(2) atom to form distorted LiO3F trigonal pyramids that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids,  an edgeedge with one V(1)O4F2 octahedra, and edges with two equivalent Li(1)O3F trigonal pyramids. The corner-sharing octahedral tilt angles are 75°. There are two shorter (2.02 Å) and one longer (2.04 Å) Li(1)-O(2) bond length. The Li(1)-F(2) bond length is 1.94 Å. V(1) is bonded to one O(2), three equivalent O(1), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, edges with two equivalent V(1)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles are 22°. The V(1)-O(2) bond length is 1.76 Å. There are two shorter (1.98 Å) and one longer (2.02 Å) V(1)-O(1) bond length. The V(1)-F(1) bond length is 1.95 Å. The V(1)-F(2) bond length is 2.09 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), three equivalent Li(1), and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Li(1), and one V(1) atom.