NaLiV4O12 crystallizes in the orthorhombic Cmmm space group. Na(1) is bonded to four equivalent O(1); four equivalent O(2); and four O(4,4) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent Li(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. Li(1) is bonded to four equivalent O(1); four equivalent O(2); and four O(3,3) atoms to form distorted LiO12 cuboctahedra that share corners with four equivalent Li(1)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra, faces with two equivalent Na(1)O12 cuboctahedra, and faces with two equivalent Li(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are six inequivalent O sites. In the first O site, O(4) is bonded in a distorted linear geometry to two equivalent Na(1) and two equivalent V(1) atoms. In the second O site, O(1) is bonded in a distorted linear geometry to one Na(1), one Li(1), and two equivalent V(1) atoms. In the third O site, O(2) is bonded in a distorted linear geometry to one Na(1), one Li(1), and two equivalent V(1) atoms. In the fourth O site, O(3) is bonded in a linear geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the fifth O site, O(4) is bonded in a distorted linear geometry to two equivalent Na(1) and two equivalent V(1) atoms. In the sixth O site, O(3) is bonded in a linear geometry to two equivalent Li(1) and two equivalent V(1) atoms.
NaLiV4O12 crystallizes in the orthorhombic Cmmm space group. Na(1) is bonded to four equivalent O(1); four equivalent O(2); and four O(4,4) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent Li(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Na(1)-O(1) bond lengths are 2.60 Å. All Na(1)-O(2) bond lengths are 2.71 Å. All Na(1)-O(4,4) bond lengths are 2.64 Å. Li(1) is bonded to four equivalent O(1); four equivalent O(2); and four O(3,3) atoms to form distorted LiO12 cuboctahedra that share corners with four equivalent Li(1)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Li(1)-O(1) bond lengths are 2.70 Å. All Li(1)-O(2) bond lengths are 2.58 Å. All Li(1)-O(3,3) bond lengths are 2.64 Å. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra, faces with two equivalent Na(1)O12 cuboctahedra, and faces with two equivalent Li(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-5°. The V(1)-O(3) bond length is 1.87 Å. The V(1)-O(4) bond length is 1.88 Å. Both V(1)-O(1) bond lengths are 1.87 Å. Both V(1)-O(2) bond lengths are 1.87 Å. There are six inequivalent O sites. In the first O site, O(4) is bonded in a distorted linear geometry to two equivalent Na(1) and two equivalent V(1) atoms. Both O(4)-V(1) bond lengths are 1.88 Å. In the second O site, O(1) is bonded in a distorted linear geometry to one Na(1), one Li(1), and two equivalent V(1) atoms. In the third O site, O(2) is bonded in a distorted linear geometry to one Na(1), one Li(1), and two equivalent V(1) atoms. In the fourth O site, O(3) is bonded in a linear geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the fifth O site, O(4) is bonded in a distorted linear geometry to two equivalent Na(1) and two equivalent V(1) atoms. In the sixth O site, O(3) is bonded in a linear geometry to two equivalent Li(1) and two equivalent V(1) atoms. Both O(3)-V(1) bond lengths are 1.87 Å.