Na2Sn2C3(O2F)3 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(6), one F(1), one F(2), and two equivalent F(3) atoms to form edge-sharing NaOF4 trigonal bipyramids. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one F(1), one F(2), and one F(3) atom. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(5), and one F(1) atom. In the second Sn site, Sn(2) is bonded in a 4-coordinate geometry to one O(3), one O(4), one F(2), and one F(3) atom. There are three inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(6) atom. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one O(2) and one O(5) atom. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Sn(1), and one C(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Sn(1) and one C(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(2), one Sn(2), and one C(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Sn(2) and one C(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one C(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Na(1), one Na(2), and one Sn(1) atom. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to one Na(1), one Na(2), and one Sn(2) atom. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Sn(2) atom to form distorted edge-sharing FNa3Sn trigonal pyramids.
Na2Sn2C3(O2F)3 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(6), one F(1), one F(2), and two equivalent F(3) atoms to form edge-sharing NaOF4 trigonal bipyramids. The Na(1)-O(6) bond length is 2.45 Å. The Na(1)-F(1) bond length is 2.47 Å. The Na(1)-F(2) bond length is 2.23 Å. There is one shorter (2.27 Å) and one longer (2.30 Å) Na(1)-F(3) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one F(1), one F(2), and one F(3) atom. The Na(2)-O(1) bond length is 2.50 Å. The Na(2)-O(3) bond length is 2.82 Å. The Na(2)-O(5) bond length is 2.42 Å. The Na(2)-O(6) bond length is 2.47 Å. The Na(2)-F(1) bond length is 2.35 Å. The Na(2)-F(2) bond length is 2.30 Å. The Na(2)-F(3) bond length is 2.83 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(5), and one F(1) atom. The Sn(1)-O(1) bond length is 2.25 Å. The Sn(1)-O(2) bond length is 2.36 Å. The Sn(1)-O(5) bond length is 2.47 Å. The Sn(1)-F(1) bond length is 2.10 Å. In the second Sn site, Sn(2) is bonded in a 4-coordinate geometry to one O(3), one O(4), one F(2), and one F(3) atom. The Sn(2)-O(3) bond length is 2.27 Å. The Sn(2)-O(4) bond length is 2.51 Å. The Sn(2)-F(2) bond length is 2.15 Å. The Sn(2)-F(3) bond length is 2.10 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(6) atom. The C(1)-O(1) bond length is 1.29 Å. The C(1)-O(6) bond length is 1.25 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one O(2) and one O(5) atom. The C(2)-O(2) bond length is 1.27 Å. The C(2)-O(5) bond length is 1.26 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(3)-O(3) bond length is 1.28 Å. The C(3)-O(4) bond length is 1.26 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Sn(1), and one C(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Sn(1) and one C(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(2), one Sn(2), and one C(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Sn(2) and one C(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one C(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Na(1), one Na(2), and one Sn(1) atom. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to one Na(1), one Na(2), and one Sn(2) atom. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Sn(2) atom to form distorted edge-sharing FNa3Sn trigonal pyramids.