TbCu4C18H12I4(NO2)3 crystallizes in the monoclinic P2_1/c space group. Tb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Tb(1)-O(1) bond length is 2.35 Å. The Tb(1)-O(2) bond length is 2.30 Å. The Tb(1)-O(3) bond length is 2.32 Å. The Tb(1)-O(4) bond length is 2.32 Å. The Tb(1)-O(5) bond length is 2.39 Å. The Tb(1)-O(6) bond length is 2.33 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one I(2), one I(4), and two equivalent I(1) atoms to form distorted corner-sharing CuI4 tetrahedra. The Cu(1)-I(2) bond length is 2.69 Å. The Cu(1)-I(4) bond length is 2.67 Å. There is one shorter (2.68 Å) and one longer (2.76 Å) Cu(1)-I(1) bond length. In the second Cu site, Cu(2) is bonded in a distorted single-bond geometry to one N(2), one I(1), one I(3), and one I(4) atom. The Cu(2)-N(2) bond length is 2.03 Å. The Cu(2)-I(1) bond length is 2.76 Å. The Cu(2)-I(3) bond length is 2.77 Å. The Cu(2)-I(4) bond length is 2.69 Å. In the third Cu site, Cu(3) is bonded in a distorted single-bond geometry to one N(3), one I(1), one I(2), and one I(3) atom. The Cu(3)-N(3) bond length is 2.05 Å. The Cu(3)-I(1) bond length is 2.76 Å. The Cu(3)-I(2) bond length is 2.71 Å. The Cu(3)-I(3) bond length is 2.71 Å. In the fourth Cu site, Cu(4) is bonded in a 1-coordinate geometry to one N(1), one I(2), one I(3), and one I(4) atom. The Cu(4)-N(1) bond length is 2.06 Å. The Cu(4)-I(2) bond length is 2.82 Å. The Cu(4)-I(3) bond length is 2.60 Å. The Cu(4)-I(4) bond length is 2.69 Å. There are eighteen inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one N(1), and one H(1) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-N(1) bond length is 1.39 Å. The C(1)-H(1) bond length is 0.95 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one H(2) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-H(2) bond length is 0.95 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(6) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-C(6) bond length is 1.55 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3) and one H(3) atom. The C(4)-H(3) bond length is 0.95 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(4) atom. The C(5)-N(1) bond length is 1.39 Å. The C(5)-H(4) bond length is 0.95 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(2) atom. The C(6)-O(1) bond length is 1.27 Å. The C(6)-O(2) bond length is 1.25 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(8), one N(2), and one H(5) atom. The C(7)-C(8) bond length is 1.39 Å. The C(7)-N(2) bond length is 1.39 Å. The C(7)-H(5) bond length is 0.95 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(7), one C(9), and one H(6) atom. The C(8)-C(9) bond length is 1.39 Å. The C(8)-H(6) bond length is 0.95 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(8) atom. The C(9)-C(10) bond length is 1.39 Å. The C(9)-C(12) bond length is 1.54 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(11), one C(9), and one H(7) atom. The C(10)-C(11) bond length is 1.39 Å. The C(10)-H(7) bond length is 0.95 Å. In the eleventh C site, C(11) is bonded in a distorted trigonal planar geometry to one C(10), one N(2), and one H(8) atom. The C(11)-N(2) bond length is 1.39 Å. The C(11)-H(8) bond length is 0.95 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(9), one O(3), and one O(4) atom. The C(12)-O(3) bond length is 1.27 Å. The C(12)-O(4) bond length is 1.26 Å. In the thirteenth C site, C(13) is bonded in a distorted bent 120 degrees geometry to one N(3) and one H(9) atom. The C(13)-N(3) bond length is 1.39 Å. The C(13)-H(9) bond length is 0.95 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(15) and one H(10) atom. The C(14)-C(15) bond length is 1.39 Å. The C(14)-H(10) bond length is 0.95 Å. In the fifteenth C site, C(15) is bonded in a trigonal planar geometry to one C(14), one C(16), and one C(18) atom. The C(15)-C(16) bond length is 1.39 Å. The C(15)-C(18) bond length is 1.54 Å. In the sixteenth C site, C(16) is bonded in a distorted single-bond geometry to one C(15), one C(17), and one H(11) atom. The C(16)-C(17) bond length is 1.39 Å. The C(16)-H(11) bond length is 0.95 Å. In the seventeenth C site, C(17) is bonded in a distorted trigonal planar geometry to one C(16), one N(3), and one H(12) atom. The C(17)-N(3) bond length is 1.39 Å. The C(17)-H(12) bond length is 0.95 Å. In the eighteenth C site, C(18) is bonded in a bent 120 degrees geometry to one C(15), one O(5), and one O(6) atom. The C(18)-O(5) bond length is 1.25 Å. The C(18)-O(6) bond length is 1.27 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(4), one C(1), and one C(5) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(2), one C(11), and one C(7) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(3), one C(13), and one C(17) atom. There are twelve 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 C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(5) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(7) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(8) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(10) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(11) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(13) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(14) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(16) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(17) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Tb(1) and one C(6) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Tb(1) and one C(6) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Tb(1) and one C(12) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Tb(1) and one C(12) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Tb(1) and one C(18) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to one Tb(1) and one C(18) atom. There are four inequivalent I sites. In the first I site, I(1) is bonded in a 4-coordinate geometry to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms. In the second I site, I(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one Cu(4) atom. In the third I site, I(3) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one Cu(4) atom. In the fourth I site, I(4) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(4) atom. Linkers: 12 [O]C(=O)c1ccncc1. Metal clusters: 4 [Tb] ,16 [Cu]. The MOF has largest included sphere 4.97 A, density 2.38 g/cm3, surface area 2318.81 m2/g, accessible volume 0.19 cm3/g