NaSb3O8 crystallizes in the orthorhombic Ibam space group. Na(1) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(2), two equivalent O(3), and four equivalent O(1) atoms to form distorted SbO7 trigonal bipyramids that share corners with two equivalent Sb(2)O8 hexagonal bipyramids, corners with two equivalent Sb(1)O7 trigonal bipyramids, edges with two equivalent Sb(2)O8 hexagonal bipyramids, and edges with two equivalent Sb(1)O7 trigonal bipyramids. In the second Sb site, Sb(2) is bonded to four equivalent O(1) and four equivalent O(2) atoms to form distorted SbO8 hexagonal bipyramids that share corners with four equivalent Sb(1)O7 trigonal bipyramids, edges with two equivalent Sb(2)O8 hexagonal bipyramids, and edges with four equivalent Sb(1)O7 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Sb(2), and two equivalent Sb(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Sb(1) and two equivalent Sb(2) atoms. In the third O site, O(3) is bonded to two equivalent Na(1) and two equivalent Sb(1) atoms to form a mixture of distorted edge and corner-sharing ONa2Sb2 tetrahedra.
NaSb3O8 crystallizes in the orthorhombic Ibam space group. Na(1) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. All Na(1)-O(1) bond lengths are 2.59 Å. All Na(1)-O(3) bond lengths are 2.53 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(2), two equivalent O(3), and four equivalent O(1) atoms to form distorted SbO7 trigonal bipyramids that share corners with two equivalent Sb(2)O8 hexagonal bipyramids, corners with two equivalent Sb(1)O7 trigonal bipyramids, edges with two equivalent Sb(2)O8 hexagonal bipyramids, and edges with two equivalent Sb(1)O7 trigonal bipyramids. The Sb(1)-O(2) bond length is 1.98 Å. There is one shorter (1.99 Å) and one longer (2.03 Å) Sb(1)-O(3) bond length. There are two shorter (2.00 Å) and two longer (2.50 Å) Sb(1)-O(1) bond lengths. In the second Sb site, Sb(2) is bonded to four equivalent O(1) and four equivalent O(2) atoms to form distorted SbO8 hexagonal bipyramids that share corners with four equivalent Sb(1)O7 trigonal bipyramids, edges with two equivalent Sb(2)O8 hexagonal bipyramids, and edges with four equivalent Sb(1)O7 trigonal bipyramids. All Sb(2)-O(1) bond lengths are 2.06 Å. All Sb(2)-O(2) bond lengths are 2.20 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Sb(2), and two equivalent Sb(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Sb(1) and two equivalent Sb(2) atoms. In the third O site, O(3) is bonded to two equivalent Na(1) and two equivalent Sb(1) atoms to form a mixture of distorted edge and corner-sharing ONa2Sb2 tetrahedra.