Na2V6O13 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 7-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(7), and three equivalent O(5) atoms. In the second V site, V(2) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 19°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), and three equivalent O(6) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a T-shaped geometry to one V(3) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1) and three equivalent V(1) atoms. In the sixth O site, O(6) is bonded to one V(2) and three equivalent V(3) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the seventh O site, O(7) is bonded to four equivalent Na(1) and two equivalent V(1) atoms to form distorted edge-sharing ONa4V2 octahedra.
Na2V6O13 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 7-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms. The Na(1)-O(5) bond length is 2.56 Å. Both Na(1)-O(1) bond lengths are 2.79 Å. Both Na(1)-O(4) bond lengths are 2.36 Å. Both Na(1)-O(7) bond lengths are 2.60 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(7), and three equivalent O(5) atoms. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(7) bond length is 1.94 Å. There are two shorter (1.97 Å) and one longer (2.03 Å) V(1)-O(5) bond length. In the second V site, V(2) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 19°. The V(2)-O(1) bond length is 2.09 Å. The V(2)-O(6) bond length is 2.03 Å. There is one shorter (1.91 Å) and one longer (1.96 Å) V(2)-O(2) bond length. Both V(2)-O(3) bond lengths are 1.92 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), and three equivalent O(6) atoms. The V(3)-O(2) bond length is 1.96 Å. The V(3)-O(3) bond length is 2.04 Å. The V(3)-O(4) bond length is 1.67 Å. There are two shorter (1.97 Å) and one longer (2.43 Å) V(3)-O(6) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a T-shaped geometry to one V(3) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1) and three equivalent V(1) atoms. In the sixth O site, O(6) is bonded to one V(2) and three equivalent V(3) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the seventh O site, O(7) is bonded to four equivalent Na(1) and two equivalent V(1) atoms to form distorted edge-sharing ONa4V2 octahedra.