TbCu4C21N4H19O7I7 crystallizes in the monoclinic P2_1/c space group. Tb(1) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. The Tb(1)-O(2) bond length is 2.36 Å. The Tb(1)-O(3) bond length is 2.25 Å. The Tb(1)-O(4) bond length is 2.35 Å. The Tb(1)-O(5) bond length is 2.56 Å. The Tb(1)-O(6) bond length is 2.33 Å. The Tb(1)-O(7) bond length is 2.35 Å. There is one shorter (2.45 Å) and one longer (2.56 Å) Tb(1)-O(1) bond length. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted single-bond geometry to one N(2), one I(2), one I(3), and one I(4) atom. The Cu(1)-N(2) bond length is 2.00 Å. The Cu(1)-I(2) bond length is 2.72 Å. The Cu(1)-I(3) bond length is 2.68 Å. The Cu(1)-I(4) bond length is 2.80 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one I(1), one I(3), and two equivalent I(2) atoms. The Cu(2)-I(1) bond length is 2.65 Å. The Cu(2)-I(3) bond length is 2.61 Å. There is one shorter (2.64 Å) and one longer (2.74 Å) Cu(2)-I(2) bond length. In the third Cu site, Cu(3) is bonded in a distorted single-bond geometry to one N(3), one I(1), one I(3), and one I(4) atom. The Cu(3)-N(3) bond length is 2.01 Å. The Cu(3)-I(1) bond length is 2.75 Å. The Cu(3)-I(3) bond length is 2.68 Å. The Cu(3)-I(4) bond length is 2.63 Å. In the fourth Cu site, Cu(4) is bonded in a distorted single-bond geometry to one N(1), one I(1), one I(2), and one I(4) atom. The Cu(4)-N(1) bond length is 2.00 Å. The Cu(4)-I(1) bond length is 2.78 Å. The Cu(4)-I(2) bond length is 2.69 Å. The Cu(4)-I(4) bond length is 2.64 Å. There are twenty-one inequivalent C sites. In the first C site, C(9) is bonded in a distorted trigonal planar geometry to one C(12), one N(3), and one H(4) atom. The C(9)-C(12) bond length is 1.39 Å. The C(9)-N(3) bond length is 1.35 Å. The C(9)-H(4) bond length is 1.09 Å. In the second C site, C(10) is bonded in a distorted trigonal planar geometry to one C(4), one N(2), and one H(5) atom. The C(10)-C(4) bond length is 1.39 Å. The C(10)-N(2) bond length is 1.35 Å. The C(10)-H(5) bond length is 1.09 Å. In the third C site, C(11) is bonded in a trigonal planar geometry to one N(4), one H(6), and one O(6) atom. The C(11)-N(4) bond length is 1.33 Å. The C(11)-H(6) bond length is 1.10 Å. The C(11)-O(6) bond length is 1.26 Å. In the fourth C site, C(12) is bonded in a distorted trigonal planar geometry to one C(7), one C(9), and one H(7) atom. The C(12)-C(7) bond length is 1.40 Å. The C(12)-H(7) bond length is 1.09 Å. In the fifth C site, C(13) is bonded in a distorted trigonal planar geometry to one C(16), one N(3), and one H(8) atom. The C(13)-C(16) bond length is 1.39 Å. The C(13)-N(3) bond length is 1.35 Å. The C(13)-H(8) bond length is 1.09 Å. In the sixth C site, C(14) is bonded in a distorted single-bond geometry to one C(15), one C(2), and one H(9) atom. The C(14)-C(15) bond length is 1.39 Å. The C(14)-C(2) bond length is 1.40 Å. The C(14)-H(9) bond length is 1.09 Å. In the seventh C site, C(15) is bonded in a distorted trigonal planar geometry to one C(14), one N(1), and one H(10) atom. The C(15)-N(1) bond length is 1.35 Å. The C(15)-H(10) bond length is 1.09 Å. In the eighth C site, C(16) is bonded in a distorted single-bond geometry to one C(13), one C(7), and one H(11) atom. The C(16)-C(7) bond length is 1.40 Å. The C(16)-H(11) bond length is 1.08 Å. In the ninth C site, C(17) is bonded in a distorted bent 120 degrees geometry to one C(7), one O(2), and one O(7) atom. The C(17)-C(7) bond length is 1.52 Å. The C(17)-O(2) bond length is 1.27 Å. The C(17)-O(7) bond length is 1.27 Å. In the tenth C site, C(18) is bonded in a distorted single-bond geometry to one C(19), one C(2), and one H(12) atom. The C(18)-C(19) bond length is 1.39 Å. The C(18)-C(2) bond length is 1.40 Å. The C(18)-H(12) bond length is 1.09 Å. In the eleventh C site, C(19) is bonded in a distorted trigonal planar geometry to one C(18), one N(1), and one H(13) atom. The C(19)-N(1) bond length is 1.35 Å. The C(19)-H(13) bond length is 1.09 Å. In the twelfth C site, C(20) is bonded to one N(4), one H(14), one H(15), and one H(16) atom to form corner-sharing CH3N tetrahedra. The C(20)-N(4) bond length is 1.46 Å. The C(20)-H(14) bond length is 1.09 Å. The C(20)-H(15) bond length is 1.10 Å. The C(20)-H(16) bond length is 1.10 Å. In the thirteenth C site, C(21) is bonded to one N(4), one H(17), one H(18), and one H(19) atom to form corner-sharing CH3N tetrahedra. The C(21)-N(4) bond length is 1.46 Å. The C(21)-H(17) bond length is 1.09 Å. The C(21)-H(18) bond length is 1.10 Å. The C(21)-H(19) bond length is 1.10 Å. In the fourteenth C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(5) atom. The C(1)-C(3) bond length is 1.50 Å. The C(1)-O(1) bond length is 1.29 Å. The C(1)-O(5) bond length is 1.27 Å. In the fifteenth C site, C(2) is bonded in a trigonal planar geometry to one C(14), one C(18), and one C(5) atom. The C(2)-C(5) bond length is 1.50 Å. In the sixteenth C site, C(3) is bonded in a trigonal planar geometry to one C(1), one C(4), and one C(8) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-C(8) bond length is 1.40 Å. In the seventeenth C site, C(4) is bonded in a distorted single-bond geometry to one C(10), one C(3), and one H(1) atom. The C(4)-H(1) bond length is 1.09 Å. In the eighteenth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(3), and one O(4) atom. The C(5)-O(3) bond length is 1.27 Å. The C(5)-O(4) bond length is 1.27 Å. In the nineteenth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(8), one N(2), and one H(2) atom. The C(6)-C(8) bond length is 1.39 Å. The C(6)-N(2) bond length is 1.35 Å. The C(6)-H(2) bond length is 1.09 Å. In the twentieth C site, C(7) is bonded in a trigonal planar geometry to one C(12), one C(16), and one C(17) atom. In the twenty-first C site, C(8) is bonded in a distorted single-bond geometry to one C(3), one C(6), and one H(3) atom. The C(8)-H(3) bond length is 1.09 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(4), one C(15), and one C(19) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(1), one C(10), and one C(6) 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(9) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(11), one C(20), and one C(21) atom. There are nineteen inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(8) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(9) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(10) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(11) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(12) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(13) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(14) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(15) 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(18) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(19) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(20) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(20) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(20) atom. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(21) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(21) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(21) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Tb(1) and one C(1) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Tb(1) and one C(17) atom. In the third O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Tb(1) and one C(17) atom. In the fourth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Tb(1) and one C(5) atom. In the fifth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Tb(1) and one C(5) atom. In the sixth O site, O(5) is bonded in a single-bond geometry to one Tb(1), one C(1), and one I(5) atom. The O(5)-I(5) bond length is 2.84 Å. In the seventh O site, O(6) is bonded in a 2-coordinate geometry to one Tb(1) and one C(11) atom. There are seven inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), one Cu(4), and one I(7) atom. The I(1)-I(7) bond length is 3.26 Å. In the second I site, I(2) is bonded in a 4-coordinate geometry to one Cu(1), one Cu(4), and two equivalent Cu(2) atoms. In the third I site, I(3) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. In the fourth I site, I(4) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one Cu(4) atom. In the fifth I site, I(5) is bonded in a distorted linear geometry to one O(5) and one I(6) atom. The I(5)-I(6) bond length is 2.73 Å. In the sixth I site, I(6) is bonded in a single-bond geometry to one I(5) atom. In the seventh I site, I(7) is bonded in a 2-coordinate geometry to one I(1) and one I(7) atom. The I(7)-I(7) bond length is 2.88 Å. Linkers: 12 [O]C(=O)c1ccncc1. Metal clusters: 4 [Tb] ,16 [Cu]. The MOF has largest included sphere 2.25 A, density 3.32 g/cm3, surface area 2163.20 m2/g, accessible volume 0.06 cm3/g