NaV5O8 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 4-coordinate geometry to four equivalent O(2) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. In the third V site, V(3) is bonded to one O(1), two equivalent O(4), and three equivalent O(3) atoms to form a mixture of face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(2), one V(3), and two equivalent V(1) atoms to form OV4 trigonal pyramids that share corners with two equivalent O(2)Na2V3 trigonal bipyramids, corners with four equivalent O(1)V4 trigonal pyramids, edges with two equivalent O(2)Na2V3 trigonal bipyramids, and  an edgeedge with one O(1)V4 trigonal pyramid. In the second O site, O(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONa2V3 trigonal bipyramids that share corners with three equivalent O(2)Na2V3 trigonal bipyramids, corners with two equivalent O(1)V4 trigonal pyramids, edges with three equivalent O(2)Na2V3 trigonal bipyramids, and edges with two equivalent O(1)V4 trigonal pyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent V(3) and three equivalent V(2) atoms.
NaV5O8 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 4-coordinate geometry to four equivalent O(2) atoms. All Na(1)-O(2) bond lengths are 2.66 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 49°. Both V(1)-O(2) bond lengths are 2.10 Å. All V(1)-O(1) bond lengths are 2.03 Å. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. The V(2)-O(1) bond length is 2.03 Å. Both V(2)-O(2) bond lengths are 2.01 Å. There is one shorter (2.00 Å) and two longer (2.26 Å) V(2)-O(4) bond lengths. In the third V site, V(3) is bonded to one O(1), two equivalent O(4), and three equivalent O(3) atoms to form a mixture of face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. The V(3)-O(1) bond length is 2.04 Å. Both V(3)-O(4) bond lengths are 2.18 Å. There are two shorter (1.99 Å) and one longer (2.02 Å) V(3)-O(3) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(2), one V(3), and two equivalent V(1) atoms to form OV4 trigonal pyramids that share corners with two equivalent O(2)Na2V3 trigonal bipyramids, corners with four equivalent O(1)V4 trigonal pyramids, edges with two equivalent O(2)Na2V3 trigonal bipyramids, and  an edgeedge with one O(1)V4 trigonal pyramid. In the second O site, O(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONa2V3 trigonal bipyramids that share corners with three equivalent O(2)Na2V3 trigonal bipyramids, corners with two equivalent O(1)V4 trigonal pyramids, edges with three equivalent O(2)Na2V3 trigonal bipyramids, and edges with two equivalent O(1)V4 trigonal pyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent V(3) and three equivalent V(2) atoms.