Ce2C12S3(NO2)6 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 10-coordinate geometry to one N(1), one N(3), one N(5), one N(6), one O(1), one O(10), one O(11), one O(12), one O(5), and one O(9) atom. The Ce(1)-N(1) bond length is 2.79 Å. The Ce(1)-N(3) bond length is 2.69 Å. The Ce(1)-N(5) bond length is 2.77 Å. The Ce(1)-N(6) bond length is 2.79 Å. The Ce(1)-O(1) bond length is 2.49 Å. The Ce(1)-O(10) bond length is 2.46 Å. The Ce(1)-O(11) bond length is 2.52 Å. The Ce(1)-O(12) bond length is 2.49 Å. The Ce(1)-O(5) bond length is 2.48 Å. The Ce(1)-O(9) bond length is 2.56 Å. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to one N(2), one N(4), one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom. The Ce(2)-N(2) bond length is 2.71 Å. The Ce(2)-N(4) bond length is 2.75 Å. The Ce(2)-O(2) bond length is 2.46 Å. The Ce(2)-O(3) bond length is 2.50 Å. The Ce(2)-O(4) bond length is 2.55 Å. The Ce(2)-O(6) bond length is 2.39 Å. The Ce(2)-O(7) bond length is 2.43 Å. The Ce(2)-O(8) bond length is 2.49 Å. There are twelve inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one N(1) atom. The C(1)-N(1) bond length is 1.29 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one N(2) atom. The C(2)-N(2) bond length is 1.32 Å. In the third C site, C(3) is bonded in a bent 120 degrees geometry to one O(1) and one O(2) atom. The C(3)-O(1) bond length is 1.29 Å. The C(3)-O(2) bond length is 1.24 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(4)-O(3) bond length is 1.17 Å. The C(4)-O(4) bond length is 1.32 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one N(3) atom. The C(5)-N(3) bond length is 1.30 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one N(4) atom. The C(6)-N(4) bond length is 1.34 Å. In the seventh C site, C(7) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(7)-O(5) bond length is 1.28 Å. The C(7)-O(6) bond length is 1.26 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one O(7) and one O(8) atom. The C(8)-O(7) bond length is 1.26 Å. The C(8)-O(8) bond length is 1.25 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one N(5) atom. The C(9)-N(5) bond length is 1.32 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one N(6) atom. The C(10)-N(6) bond length is 1.34 Å. In the eleventh C site, C(11) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(9) atom. The C(11)-O(10) bond length is 1.23 Å. The C(11)-O(9) bond length is 1.26 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one O(11) and one O(12) atom. The C(12)-O(11) bond length is 1.19 Å. The C(12)-O(12) bond length is 1.27 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a distorted water-like geometry to one Ce(1), one C(1), and one S(1) atom. The N(1)-S(1) bond length is 1.62 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Ce(2), one C(2), and one S(1) atom. The N(2)-S(1) bond length is 1.62 Å. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Ce(1), one C(5), and one S(2) atom. The N(3)-S(2) bond length is 1.64 Å. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Ce(2), one C(6), and one S(2) atom. The N(4)-S(2) bond length is 1.57 Å. In the fifth N site, N(5) is bonded in a 2-coordinate geometry to one Ce(1), one C(9), and one S(3) atom. The N(5)-S(3) bond length is 1.61 Å. In the sixth N site, N(6) is bonded in a 2-coordinate geometry to one Ce(1), one C(10), and one S(3) atom. The N(6)-S(3) bond length is 1.60 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one N(1) and one N(2) atom. In the second S site, S(2) is bonded in a water-like geometry to one N(3) and one N(4) atom. In the third S site, S(3) is bonded in an L-shaped geometry to one N(5) and one N(6) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ce(1) and one C(3) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Ce(2) and one C(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ce(2) and one C(4) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Ce(2) and one C(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Ce(1) and one C(7) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ce(2) and one C(7) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ce(2) and one C(8) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Ce(2) and one C(8) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ce(1) and one C(11) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ce(1) and one C(11) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one C(12) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Ce(1) and one C(12) atom. Linkers: 6 [O]C(=O)c1nsnc1C([O])=O. Metal clusters: 4 [Ce]. The MOF has largest included sphere 4.24 A, density 2.21 g/cm3, surface area 2171.35 m2/g, accessible volume 0.14 cm3/g