Na5Sm4Cu8C48H48(NO6)8 crystallizes in the tetragonal P-42_1c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted T-shaped geometry to one O(10), one O(3), and one O(8) atom. The Na(1)-O(10) bond length is 2.45 Å. The Na(1)-O(3) bond length is 2.33 Å. The Na(1)-O(8) bond length is 2.48 Å. In the second Na site, Na(2) is bonded in a rectangular see-saw-like geometry to four equivalent O(9) atoms. All Na(2)-O(9) bond lengths are 2.47 Å. Sm(1) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(2), one O(4), and one O(5) atom. The Sm(1)-O(1) bond length is 2.55 Å. The Sm(1)-O(11) bond length is 2.42 Å. The Sm(1)-O(2) bond length is 2.56 Å. The Sm(1)-O(4) bond length is 2.43 Å. The Sm(1)-O(5) bond length is 2.43 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a trigonal bipyramidal geometry to one N(1), one O(1), one O(3), one O(6), and one O(7) atom. The Cu(1)-N(1) bond length is 2.01 Å. The Cu(1)-O(1) bond length is 2.16 Å. The Cu(1)-O(3) bond length is 2.03 Å. The Cu(1)-O(6) bond length is 2.03 Å. The Cu(1)-O(7) bond length is 1.92 Å. In the second Cu site, Cu(2) is bonded in a trigonal bipyramidal geometry to one N(2), one O(10), one O(12), one O(8), and one O(9) atom. The Cu(2)-N(2) bond length is 2.02 Å. The Cu(2)-O(10) bond length is 1.93 Å. The Cu(2)-O(12) bond length is 1.95 Å. The Cu(2)-O(8) bond length is 1.98 Å. The Cu(2)-O(9) bond length is 2.18 Å. There are twelve inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.52 Å. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(2) bond length is 1.23 Å. In the second C site, C(2) is bonded in a 3-coordinate geometry to one C(1); one N(1); and two equivalent H(1,2) atoms. The C(2)-N(1) bond length is 1.47 Å. Both C(2)-H(1,2) bond lengths are 0.97 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(4), one O(3), and one O(4) atom. The C(3)-C(4) bond length is 1.48 Å. The C(3)-O(3) bond length is 1.29 Å. The C(3)-O(4) bond length is 1.24 Å. In the fourth C site, C(4) is bonded in a 3-coordinate geometry to one C(3), one N(1), one H(3), and one H(4) atom. The C(4)-N(1) bond length is 1.47 Å. The C(4)-H(3) bond length is 0.97 Å. The C(4)-H(4) bond length is 0.97 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(6), one O(5), and one O(6) atom. The C(5)-C(6) bond length is 1.50 Å. The C(5)-O(5) bond length is 1.24 Å. The C(5)-O(6) bond length is 1.27 Å. In the sixth C site, C(6) is bonded in a 3-coordinate geometry to one C(5); one N(1); and two equivalent H(5,6) atoms. The C(6)-N(1) bond length is 1.51 Å. Both C(6)-H(5,6) bond lengths are 0.97 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(8), one O(7), and one O(8) atom. The C(7)-C(8) bond length is 1.48 Å. The C(7)-O(7) bond length is 1.26 Å. The C(7)-O(8) bond length is 1.27 Å. In the eighth C site, C(8) is bonded in a 3-coordinate geometry to one C(7); one N(2); and two equivalent H(7,8) atoms. The C(8)-N(2) bond length is 1.48 Å. Both C(8)-H(7,8) bond lengths are 0.97 Å. In the ninth C site, C(9) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(9) atom. The C(9)-O(10) bond length is 1.25 Å. The C(9)-O(9) bond length is 1.25 Å. In the tenth C site, C(10) is bonded in a 3-coordinate geometry to one N(2), one H(10), and one H(9) atom. The C(10)-N(2) bond length is 1.46 Å. The C(10)-H(10) bond length is 0.97 Å. The C(10)-H(9) bond length is 0.97 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(12), one O(11), and one O(12) atom. The C(11)-C(12) bond length is 1.48 Å. The C(11)-O(11) bond length is 1.25 Å. The C(11)-O(12) bond length is 1.27 Å. In the twelfth C site, C(12) is bonded in a 3-coordinate geometry to one C(11), one N(2), one H(11), and one H(12) atom. The C(12)-N(2) bond length is 1.49 Å. The C(12)-H(11) bond length is 0.97 Å. The C(12)-H(12) bond length is 0.97 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a tetrahedral geometry to one Cu(1), one C(2), one C(4), and one C(6) atom. In the second N site, N(2) is bonded in a tetrahedral geometry to one Cu(2), one C(10), one C(12), and one C(8) atom. There are nine inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(4) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(5,6) is bonded in a single-bond geometry to one C(6) atom. In the fifth H site, H(7,8) is bonded in a single-bond geometry to one C(8) atom. In the sixth H site, H(9) is bonded in a single-bond geometry to one C(10) atom. In the seventh H site, H(10) is bonded in a single-bond geometry to one C(10) atom. In the eighth H site, H(11) is bonded in a single-bond geometry to one C(12) atom. In the ninth H site, H(12) is bonded in a single-bond geometry to one C(12) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Sm(1), one Cu(1), and one C(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Sm(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one C(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one C(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one C(5) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(5) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(7) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Cu(2), and one C(7) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Cu(2), and one C(9) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Cu(2), and one C(9) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one C(11) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(11) atom. Linkers: 16 [O]C(=O)CN(CC([O])=O)CC([O])=O. Metal clusters: 10 [Na] ,8 [Sm] ,16 [Cu]. The MOF has largest included sphere 10.48 A, density 1.23 g/cm3, surface area 3088.87 m2/g, accessible volume 0.43 cm3/g