NaV2O4 crystallizes in the monoclinic Pm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), two equivalent O(11), two equivalent O(14), and two equivalent O(7) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(3), one O(4), two equivalent O(10), two equivalent O(15), and two equivalent O(6) atoms. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(16), two equivalent O(5), and two equivalent O(9) atoms. In the fourth Na site, Na(4) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(12), two equivalent O(13), and two equivalent O(8) atoms. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), two equivalent O(14), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second V site, V(2) is bonded to one O(10), one O(14), two equivalent O(3), and two equivalent O(9) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the third V site, V(3) is bonded to one O(13), one O(9), two equivalent O(10), and two equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the fourth V site, V(4) is bonded to one O(12), one O(16), two equivalent O(1), and two equivalent O(11) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the fifth V site, V(5) is bonded to one O(1), one O(6), two equivalent O(13), and two equivalent O(5) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the sixth V site, V(6) is bonded to one O(2), one O(7), two equivalent O(16), and two equivalent O(8) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the seventh V site, V(7) is bonded to one O(3), one O(8), two equivalent O(15), and two equivalent O(7) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the eighth V site, V(8) is bonded to one O(11), one O(15), two equivalent O(12), and two equivalent O(4) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), one Na(4), one V(5), and two equivalent V(4) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the second O site, O(2) is bonded to one Na(3), one Na(4), one V(6), and two equivalent V(3) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one V(7), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one V(1), and two equivalent V(8) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the fifth O site, O(5) is bonded to two equivalent Na(3), one V(1), and two equivalent V(5) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the sixth O site, O(6) is bonded to two equivalent Na(2), one V(5), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the seventh O site, O(7) is bonded to two equivalent Na(1), one V(6), and two equivalent V(7) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the eighth O site, O(8) is bonded to two equivalent Na(4), one V(7), and two equivalent V(6) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the ninth O site, O(9) is bonded to two equivalent Na(3), one V(3), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the tenth O site, O(10) is bonded to two equivalent Na(2), one V(2), and two equivalent V(3) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the eleventh O site, O(11) is bonded to two equivalent Na(1), one V(8), and two equivalent V(4) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the twelfth O site, O(12) is bonded to two equivalent Na(4), one V(4), and two equivalent V(8) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the thirteenth O site, O(13) is bonded in a 5-coordinate geometry to two equivalent Na(4), one V(3), and two equivalent V(5) atoms. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to two equivalent Na(1), one V(2), and two equivalent V(1) atoms. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to two equivalent Na(2), one V(8), and two equivalent V(7) atoms. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to two equivalent Na(3), one V(4), and two equivalent V(6) atoms.
NaV2O4 crystallizes in the monoclinic Pm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), two equivalent O(11), two equivalent O(14), and two equivalent O(7) atoms. The Na(1)-O(3) bond length is 2.61 Å. The Na(1)-O(4) bond length is 2.55 Å. Both Na(1)-O(11) bond lengths are 2.42 Å. Both Na(1)-O(14) bond lengths are 2.63 Å. Both Na(1)-O(7) bond lengths are 2.38 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(3), one O(4), two equivalent O(10), two equivalent O(15), and two equivalent O(6) atoms. The Na(2)-O(3) bond length is 2.55 Å. The Na(2)-O(4) bond length is 2.58 Å. Both Na(2)-O(10) bond lengths are 2.40 Å. Both Na(2)-O(15) bond lengths are 2.64 Å. Both Na(2)-O(6) bond lengths are 2.39 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(16), two equivalent O(5), and two equivalent O(9) atoms. The Na(3)-O(1) bond length is 2.62 Å. The Na(3)-O(2) bond length is 2.55 Å. Both Na(3)-O(16) bond lengths are 2.62 Å. Both Na(3)-O(5) bond lengths are 2.39 Å. Both Na(3)-O(9) bond lengths are 2.39 Å. In the fourth Na site, Na(4) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(12), two equivalent O(13), and two equivalent O(8) atoms. The Na(4)-O(1) bond length is 2.56 Å. The Na(4)-O(2) bond length is 2.61 Å. Both Na(4)-O(12) bond lengths are 2.41 Å. Both Na(4)-O(13) bond lengths are 2.63 Å. Both Na(4)-O(8) bond lengths are 2.38 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), two equivalent O(14), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The V(1)-O(4) bond length is 2.03 Å. The V(1)-O(5) bond length is 2.00 Å. Both V(1)-O(14) bond lengths are 2.03 Å. Both V(1)-O(6) bond lengths are 2.03 Å. In the second V site, V(2) is bonded to one O(10), one O(14), two equivalent O(3), and two equivalent O(9) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The V(2)-O(10) bond length is 2.02 Å. The V(2)-O(14) bond length is 2.01 Å. Both V(2)-O(3) bond lengths are 2.00 Å. Both V(2)-O(9) bond lengths are 2.02 Å. In the third V site, V(3) is bonded to one O(13), one O(9), two equivalent O(10), and two equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The V(3)-O(13) bond length is 2.02 Å. The V(3)-O(9) bond length is 2.01 Å. Both V(3)-O(10) bond lengths are 2.02 Å. Both V(3)-O(2) bond lengths are 1.99 Å. In the fourth V site, V(4) is bonded to one O(12), one O(16), two equivalent O(1), and two equivalent O(11) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(4)-O(12) bond length is 2.00 Å. The V(4)-O(16) bond length is 1.88 Å. Both V(4)-O(1) bond lengths are 1.98 Å. Both V(4)-O(11) bond lengths are 2.01 Å. In the fifth V site, V(5) is bonded to one O(1), one O(6), two equivalent O(13), and two equivalent O(5) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The V(5)-O(1) bond length is 2.06 Å. The V(5)-O(6) bond length is 1.99 Å. Both V(5)-O(13) bond lengths are 2.03 Å. Both V(5)-O(5) bond lengths are 2.03 Å. In the sixth V site, V(6) is bonded to one O(2), one O(7), two equivalent O(16), and two equivalent O(8) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(6)-O(2) bond length is 2.05 Å. The V(6)-O(7) bond length is 2.01 Å. Both V(6)-O(16) bond lengths are 2.10 Å. Both V(6)-O(8) bond lengths are 2.02 Å. In the seventh V site, V(7) is bonded to one O(3), one O(8), two equivalent O(15), and two equivalent O(7) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(7)-O(3) bond length is 2.02 Å. The V(7)-O(8) bond length is 1.96 Å. Both V(7)-O(15) bond lengths are 2.03 Å. Both V(7)-O(7) bond lengths are 2.02 Å. In the eighth V site, V(8) is bonded to one O(11), one O(15), two equivalent O(12), and two equivalent O(4) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(8)-O(11) bond length is 2.02 Å. The V(8)-O(15) bond length is 2.02 Å. Both V(8)-O(12) bond lengths are 2.04 Å. Both V(8)-O(4) bond lengths are 2.01 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), one Na(4), one V(5), and two equivalent V(4) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the second O site, O(2) is bonded to one Na(3), one Na(4), one V(6), and two equivalent V(3) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one V(7), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one V(1), and two equivalent V(8) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the fifth O site, O(5) is bonded to two equivalent Na(3), one V(1), and two equivalent V(5) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the sixth O site, O(6) is bonded to two equivalent Na(2), one V(5), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the seventh O site, O(7) is bonded to two equivalent Na(1), one V(6), and two equivalent V(7) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the eighth O site, O(8) is bonded to two equivalent Na(4), one V(7), and two equivalent V(6) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 trigonal bipyramids. In the ninth O site, O(9) is bonded to two equivalent Na(3), one V(3), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the tenth O site, O(10) is bonded to two equivalent Na(2), one V(2), and two equivalent V(3) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the eleventh O site, O(11) is bonded to two equivalent Na(1), one V(8), and two equivalent V(4) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the twelfth O site, O(12) is bonded to two equivalent Na(4), one V(4), and two equivalent V(8) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the thirteenth O site, O(13) is bonded in a 5-coordinate geometry to two equivalent Na(4), one V(3), and two equivalent V(5) atoms. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to two equivalent Na(1), one V(2), and two equivalent V(1) atoms. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to two equivalent Na(2), one V(8), and two equivalent V(7) atoms. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to two equivalent Na(3), one V(4), and two equivalent V(6) atoms.