NaCeS2O9 crystallizes in the trigonal P3_121 space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Ce(1) is bonded in a 9-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. S(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are five inequivalent O sites. In the first O site, O(5) is bonded in a single-bond geometry to one Ce(1) atom. In the second O site, O(1) is bonded in a 1-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom. In the fourth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom. In the fifth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom.
NaCeS2O9 crystallizes in the trigonal P3_121 space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Na(1)-O(1) bond lengths are 2.92 Å. Both Na(1)-O(2) bond lengths are 2.59 Å. Both Na(1)-O(3) bond lengths are 2.43 Å. Both Na(1)-O(4) bond lengths are 2.46 Å. Ce(1) is bonded in a 9-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. The Ce(1)-O(5) bond length is 2.08 Å. Both Ce(1)-O(1) bond lengths are 2.49 Å. Both Ce(1)-O(2) bond lengths are 2.43 Å. Both Ce(1)-O(3) bond lengths are 2.57 Å. Both Ce(1)-O(4) bond lengths are 2.56 Å. S(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.50 Å. The S(1)-O(3) bond length is 1.49 Å. The S(1)-O(4) bond length is 1.49 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded in a single-bond geometry to one Ce(1) atom. In the second O site, O(1) is bonded in a 1-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom. In the fourth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom. In the fifth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Ce(1), and one S(1) atom.