NaLa3(S2O9)3 crystallizes in the orthorhombic Cmce space group. Na(1) is bonded in a 8-coordinate geometry to one O(13), one O(15), two equivalent O(12), two equivalent O(4), and two equivalent O(6) atoms. The Na(1)-O(13) bond length is 2.47 Å. The Na(1)-O(15) bond length is 2.48 Å. Both Na(1)-O(12) bond lengths are 2.56 Å. Both Na(1)-O(4) bond lengths are 2.64 Å. Both Na(1)-O(6) bond lengths are 2.57 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The La(1)-O(1) bond length is 2.72 Å. The La(1)-O(10) bond length is 2.47 Å. The La(1)-O(2) bond length is 2.58 Å. The La(1)-O(3) bond length is 2.56 Å. The La(1)-O(4) bond length is 2.51 Å. The La(1)-O(5) bond length is 2.61 Å. The La(1)-O(6) bond length is 2.70 Å. The La(1)-O(7) bond length is 2.45 Å. The La(1)-O(8) bond length is 2.69 Å. In the second La site, La(2) is bonded in a 9-coordinate geometry to one O(13), one O(14), one O(15), two equivalent O(11), two equivalent O(12), and two equivalent O(9) atoms. The La(2)-O(13) bond length is 2.61 Å. The La(2)-O(14) bond length is 2.43 Å. The La(2)-O(15) bond length is 2.82 Å. Both La(2)-O(11) bond lengths are 2.44 Å. Both La(2)-O(12) bond lengths are 2.53 Å. Both La(2)-O(9) bond lengths are 2.48 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a tetrahedral geometry to one O(3), one O(5), one O(6), and one O(8) atom. The S(1)-O(3) bond length is 1.47 Å. The S(1)-O(5) bond length is 1.47 Å. The S(1)-O(6) bond length is 1.47 Å. The S(1)-O(8) bond length is 1.46 Å. In the second S site, S(2) is bonded in a tetrahedral geometry to one O(13), one O(14), and two equivalent O(4) atoms. The S(2)-O(13) bond length is 1.46 Å. The S(2)-O(14) bond length is 1.44 Å. Both S(2)-O(4) bond lengths are 1.46 Å. In the third S site, S(3) is bonded in a tetrahedral geometry to two equivalent O(7) and two equivalent O(9) atoms. Both S(3)-O(7) bond lengths are 1.48 Å. Both S(3)-O(9) bond lengths are 1.46 Å. In the fourth S site, S(4) is bonded in a tetrahedral geometry to two equivalent O(1) and two equivalent O(2) atoms. Both S(4)-O(1) bond lengths are 1.49 Å. Both S(4)-O(2) bond lengths are 1.47 Å. In the fifth S site, S(5) is bonded in a tetrahedral geometry to two equivalent O(10) and two equivalent O(11) atoms. Both S(5)-O(10) bond lengths are 1.46 Å. Both S(5)-O(11) bond lengths are 1.45 Å. There are fifteen inequivalent O sites. In the first O site, O(13) is bonded in a distorted single-bond geometry to one Na(1), one La(2), and one S(2) atom. In the second O site, O(14) is bonded in a distorted linear geometry to one La(2) and one S(2) atom. In the third O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one La(2) atom. In the fourth O site, O(1) is bonded in a distorted single-bond geometry to one La(1) and one S(4) atom. In the fifth O site, O(2) is bonded in a distorted water-like geometry to one La(1) and one S(4) atom. In the sixth O site, O(3) is bonded in a distorted water-like geometry to one La(1) and one S(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one S(2) atom. In the eighth O site, O(5) is bonded in a distorted single-bond geometry to one La(1) and one S(1) atom. In the ninth O site, O(6) is bonded in a distorted single-bond geometry to one Na(1), one La(1), and one S(1) atom. In the tenth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one La(1) and one S(3) atom. In the eleventh O site, O(8) is bonded in a distorted single-bond geometry to one La(1) and one S(1) atom. In the twelfth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one La(2) and one S(3) atom. In the thirteenth O site, O(10) is bonded in a bent 150 degrees geometry to one La(1) and one S(5) atom. In the fourteenth O site, O(11) is bonded in a distorted linear geometry to one La(2) and one S(5) atom. In the fifteenth O site, O(12) is bonded in a water-like geometry to one Na(1) and one La(2) atom. Linkers: 48 [O]S([O])(=O)=O. Metal clusters: 8 [Na] ,24 [La]. The MOF has largest included sphere 5.12 A, density 2.72 g/cm3, surface area 1851.41 m2/g, accessible volume 0.10 cm3/g