NaN(SO2F)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to one N(1), one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. N(1) is bonded in a 3-coordinate geometry to one Na(1), one S(1), and one S(2) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded to one N(1), one O(1), one O(3), and one F(1) atom to form corner-sharing SNO2F tetrahedra. In the second S site, S(2) is bonded to one N(1), one O(2), one O(4), and one F(2) atom to form corner-sharing SNO2F tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one S(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one S(2) atom.
NaN(SO2F)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to one N(1), one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. The Na(1)-N(1) bond length is 2.78 Å. The Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(4) bond length is 2.43 Å. There is one shorter (2.49 Å) and one longer (2.73 Å) Na(1)-O(2) bond length. There is one shorter (2.38 Å) and one longer (2.91 Å) Na(1)-O(3) bond length. N(1) is bonded in a 3-coordinate geometry to one Na(1), one S(1), and one S(2) atom. The N(1)-S(1) bond length is 1.58 Å. The N(1)-S(2) bond length is 1.58 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one N(1), one O(1), one O(3), and one F(1) atom to form corner-sharing SNO2F tetrahedra. The S(1)-O(1) bond length is 1.43 Å. The S(1)-O(3) bond length is 1.44 Å. The S(1)-F(1) bond length is 1.60 Å. In the second S site, S(2) is bonded to one N(1), one O(2), one O(4), and one F(2) atom to form corner-sharing SNO2F tetrahedra. The S(2)-O(2) bond length is 1.45 Å. The S(2)-O(4) bond length is 1.43 Å. The S(2)-F(2) bond length is 1.60 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one S(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one S(2) atom.