Na2Nb2W2O13 crystallizes in the orthorhombic Imm2 space group. Na(1) is bonded to one O(3), one O(6), one O(7), two equivalent O(1), and two equivalent O(4) atoms to form NaO7 hexagonal pyramids that share  a cornercorner with one Na(1)O7 hexagonal pyramid,  an edgeedge with one Na(1)O7 hexagonal pyramid, edges with two equivalent W(1)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. Nb(1) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent W(1)O6 octahedra, and edges with four equivalent Na(1)O7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 37-45°. W(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, and edges with two equivalent Na(1)O7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 34-39°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Nb(1), and one W(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent W(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Nb(1), and one W(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent W(1) atoms. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Nb(1) atoms. In the seventh O site, O(7) is bonded in an L-shaped geometry to two equivalent Na(1) atoms.
Na2Nb2W2O13 crystallizes in the orthorhombic Imm2 space group. Na(1) is bonded to one O(3), one O(6), one O(7), two equivalent O(1), and two equivalent O(4) atoms to form NaO7 hexagonal pyramids that share  a cornercorner with one Na(1)O7 hexagonal pyramid,  an edgeedge with one Na(1)O7 hexagonal pyramid, edges with two equivalent W(1)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The Na(1)-O(3) bond length is 2.65 Å. The Na(1)-O(6) bond length is 2.66 Å. The Na(1)-O(7) bond length is 2.56 Å. Both Na(1)-O(1) bond lengths are 2.71 Å. Both Na(1)-O(4) bond lengths are 2.71 Å. Nb(1) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent W(1)O6 octahedra, and edges with four equivalent Na(1)O7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 37-45°. The Nb(1)-O(3) bond length is 2.00 Å. The Nb(1)-O(6) bond length is 2.00 Å. Both Nb(1)-O(1) bond lengths are 1.98 Å. Both Nb(1)-O(4) bond lengths are 2.03 Å. W(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, and edges with two equivalent Na(1)O7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 34-39°. The W(1)-O(2) bond length is 1.95 Å. The W(1)-O(5) bond length is 1.98 Å. Both W(1)-O(1) bond lengths are 1.94 Å. Both W(1)-O(4) bond lengths are 1.92 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Nb(1), and one W(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent W(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Nb(1), and one W(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent W(1) atoms. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Nb(1) atoms. In the seventh O site, O(7) is bonded in an L-shaped geometry to two equivalent Na(1) atoms.