SmC6H6(NO4)2 crystallizes in the monoclinic P2_1/c space group. Sm(1) is bonded in a 9-coordinate geometry to one N(2), one O(1), one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Sm(1)-N(2) bond length is 2.63 Å. The Sm(1)-O(1) bond length is 2.44 Å. The Sm(1)-O(2) bond length is 2.50 Å. The Sm(1)-O(3) bond length is 2.45 Å. The Sm(1)-O(4) bond length is 2.48 Å. The Sm(1)-O(5) bond length is 2.47 Å. The Sm(1)-O(6) bond length is 2.37 Å. The Sm(1)-O(7) bond length is 2.62 Å. The Sm(1)-O(8) bond length is 2.47 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(1), and one H(1) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-N(1) bond length is 1.35 Å. The C(1)-H(1) bond length is 1.09 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(5) atom. The C(2)-C(3) bond length is 1.43 Å. The C(2)-C(5) bond length is 1.48 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2) and one N(2) atom. The C(3)-N(2) bond length is 1.34 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(5) atom. The C(4)-O(1) bond length is 1.27 Å. The C(4)-O(5) bond length is 1.27 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(6), and one O(7) atom. The C(5)-O(6) bond length is 1.27 Å. The C(5)-O(7) bond length is 1.28 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one O(2) and one O(8) atom. The C(6)-O(2) bond length is 1.26 Å. The C(6)-O(8) bond length is 1.27 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one C(1), one N(2), and one H(2) atom. The N(1)-N(2) bond length is 1.34 Å. The N(1)-H(2) bond length is 1.02 Å. In the second N site, N(2) is bonded in a distorted single-bond geometry to one Sm(1), one C(3), and one N(1) atom. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(1) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(3) atom. The H(3)-O(3) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a distorted single-bond geometry to one O(3) and one O(7) atom. The H(4)-O(3) bond length is 1.00 Å. The H(4)-O(7) bond length is 1.70 Å. In the fifth H site, H(5) is bonded in a distorted single-bond geometry to one O(4) and one O(8) atom. The H(5)-O(4) bond length is 1.00 Å. The H(5)-O(8) bond length is 1.70 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(4) atom. The H(6)-O(4) bond length is 0.98 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Sm(1) and one C(4) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Sm(1) and one C(6) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to one Sm(1), one H(3), and one H(4) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Sm(1), one H(5), and one H(6) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one C(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one C(5) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Sm(1), one C(5), and one H(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Sm(1), one C(6), and one H(5) atom. Linkers: 2 [O]C(=O)C([O])=O ,4 [O]C(=O)c1c[nH]nc1C([O])=O. Metal clusters: 4 [Sm]. The MOF has largest included sphere 2.22 A, density 2.57 g/cm3, surface area 2265.88 m2/g, accessible volume 0.05 cm3/g