NaSb2(OF3)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to one O(2), one F(1), one F(6), two equivalent F(3), and two equivalent F(4) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(1), one F(1), one F(3), and two equivalent F(2) atoms to form distorted SbOF4 square pyramids that share  a cornercorner with one Sb(2)O2F3 trigonal bipyramid and  an edgeedge with one Sb(1)OF4 square pyramid. In the second Sb site, Sb(2) is bonded to one O(1), one O(2), one F(4), one F(5), and one F(6) atom to form corner-sharing SbO2F3 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Sb(1) and one Sb(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1) and one Sb(2) atom. There are six inequivalent F sites. In the first F site, F(4) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one Sb(2) atom. In the second F site, F(5) is bonded in a single-bond geometry to one Sb(2) atom. In the third F site, F(6) is bonded in a bent 120 degrees geometry to one Na(1) and one Sb(2) atom. In the fourth F site, F(1) is bonded in a water-like geometry to one Na(1) and one Sb(1) atom. In the fifth F site, F(2) is bonded in a bent 120 degrees geometry to two equivalent Sb(1) atoms. In the sixth F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one Sb(1) atom.
NaSb2(OF3)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to one O(2), one F(1), one F(6), two equivalent F(3), and two equivalent F(4) atoms. The Na(1)-O(2) bond length is 2.35 Å. The Na(1)-F(1) bond length is 2.51 Å. The Na(1)-F(6) bond length is 2.34 Å. There is one shorter (2.35 Å) and one longer (2.58 Å) Na(1)-F(3) bond length. There is one shorter (2.55 Å) and one longer (2.80 Å) Na(1)-F(4) bond length. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(1), one F(1), one F(3), and two equivalent F(2) atoms to form distorted SbOF4 square pyramids that share  a cornercorner with one Sb(2)O2F3 trigonal bipyramid and  an edgeedge with one Sb(1)OF4 square pyramid. The Sb(1)-O(1) bond length is 1.96 Å. The Sb(1)-F(1) bond length is 1.92 Å. The Sb(1)-F(3) bond length is 1.97 Å. There is one shorter (2.19 Å) and one longer (2.20 Å) Sb(1)-F(2) bond length. In the second Sb site, Sb(2) is bonded to one O(1), one O(2), one F(4), one F(5), and one F(6) atom to form corner-sharing SbO2F3 trigonal bipyramids. The Sb(2)-O(1) bond length is 2.00 Å. The Sb(2)-O(2) bond length is 1.85 Å. The Sb(2)-F(4) bond length is 1.98 Å. The Sb(2)-F(5) bond length is 1.92 Å. The Sb(2)-F(6) bond length is 1.94 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Sb(1) and one Sb(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1) and one Sb(2) atom. There are six inequivalent F sites. In the first F site, F(4) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one Sb(2) atom. In the second F site, F(5) is bonded in a single-bond geometry to one Sb(2) atom. In the third F site, F(6) is bonded in a bent 120 degrees geometry to one Na(1) and one Sb(2) atom. In the fourth F site, F(1) is bonded in a water-like geometry to one Na(1) and one Sb(1) atom. In the fifth F site, F(2) is bonded in a bent 120 degrees geometry to two equivalent Sb(1) atoms. In the sixth F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one Sb(1) atom.