Tb2Cu6C15H27(N2O7)3 crystallizes in the trigonal R-3 space group. The structure consists of a Tb2Cu6C15H27(N2O7)3 framework. There are two inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 9-coordinate geometry to one O(1), one O(11), one O(13), one O(14), one O(15), one O(3), one O(5), one O(7), and one O(9) atom. The Tb(1)-O(1) bond length is 2.48 Å. The Tb(1)-O(11) bond length is 2.43 Å. The Tb(1)-O(13) bond length is 2.41 Å. The Tb(1)-O(14) bond length is 2.45 Å. The Tb(1)-O(15) bond length is 2.39 Å. The Tb(1)-O(3) bond length is 2.45 Å. The Tb(1)-O(5) bond length is 2.45 Å. The Tb(1)-O(7) bond length is 2.48 Å. The Tb(1)-O(9) bond length is 2.44 Å. In the second Tb site, Tb(2) is bonded in a 3-coordinate geometry to one O(17), one O(19), and one O(21) atom. The Tb(2)-O(17) bond length is 2.33 Å. The Tb(2)-O(19) bond length is 2.38 Å. The Tb(2)-O(21) bond length is 2.35 Å. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square pyramidal geometry to one N(1), one O(1), one O(13), one O(16), and one O(4) atom. The Cu(1)-N(1) bond length is 1.97 Å. The Cu(1)-O(1) bond length is 1.99 Å. The Cu(1)-O(13) bond length is 1.95 Å. The Cu(1)-O(16) bond length is 1.96 Å. The Cu(1)-O(4) bond length is 2.33 Å. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to one N(2), one O(14), one O(3), and one O(6) atom. The Cu(2)-N(2) bond length is 1.97 Å. The Cu(2)-O(14) bond length is 1.93 Å. The Cu(2)-O(3) bond length is 1.98 Å. The Cu(2)-O(6) bond length is 2.29 Å. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to one N(3), one O(15), one O(2), and one O(5) atom. The Cu(3)-N(3) bond length is 1.96 Å. The Cu(3)-O(15) bond length is 1.94 Å. The Cu(3)-O(2) bond length is 2.32 Å. The Cu(3)-O(5) bond length is 1.97 Å. In the fourth Cu site, Cu(4) is bonded in a rectangular see-saw-like geometry to one N(4), one O(10), one O(13), and one O(7) atom. The Cu(4)-N(4) bond length is 1.97 Å. The Cu(4)-O(10) bond length is 2.36 Å. The Cu(4)-O(13) bond length is 1.95 Å. The Cu(4)-O(7) bond length is 1.96 Å. In the fifth Cu site, Cu(5) is bonded in a square pyramidal geometry to one N(5), one O(12), one O(14), one O(18), and one O(9) atom. The Cu(5)-N(5) bond length is 1.95 Å. The Cu(5)-O(12) bond length is 2.31 Å. The Cu(5)-O(14) bond length is 1.95 Å. The Cu(5)-O(18) bond length is 1.94 Å. The Cu(5)-O(9) bond length is 2.00 Å. In the sixth Cu site, Cu(6) is bonded in a square pyramidal geometry to one N(6), one O(11), one O(15), one O(20), and one O(8) atom. The Cu(6)-N(6) bond length is 1.96 Å. The Cu(6)-O(11) bond length is 1.99 Å. The Cu(6)-O(15) bond length is 1.96 Å. The Cu(6)-O(20) bond length is 1.96 Å. The Cu(6)-O(8) bond length is 2.32 Å. There are fifteen inequivalent C sites. In the first C site, C(11) is bonded in a trigonal planar geometry to one H(21), one O(16), and one O(17) atom. The C(11)-H(21) bond length is 0.93 Å. The C(11)-O(16) bond length is 1.28 Å. The C(11)-O(17) bond length is 1.25 Å. In the second C site, C(12) is bonded in a trigonal planar geometry to one H(22), one O(18), and one O(19) atom. The C(12)-H(22) bond length is 0.93 Å. The C(12)-O(18) bond length is 1.22 Å. The C(12)-O(19) bond length is 1.23 Å. In the third C site, C(13) is bonded in a trigonal planar geometry to one H(23), one O(20), and one O(21) atom. The C(13)-H(23) bond length is 0.93 Å. The C(13)-O(20) bond length is 1.25 Å. The C(13)-O(21) bond length is 1.25 Å. In the fourth C site, C(14) is bonded in a distorted trigonal non-coplanar geometry to one N(3) and two equivalent H(24,25) atoms. The C(14)-N(3) bond length is 1.43 Å. Both C(14)-H(24,25) bond lengths are 0.97 Å. In the fifth C site, C(15) is bonded in a 3-coordinate geometry to one C(1), one N(1), one H(26), and one H(27) atom. The C(15)-C(1) bond length is 1.47 Å. The C(15)-N(1) bond length is 1.46 Å. The C(15)-H(26) bond length is 0.97 Å. The C(15)-H(27) bond length is 0.97 Å. In the sixth C site, C(1) is bonded in a distorted trigonal planar geometry to one C(15), one O(1), and one O(2) atom. The C(1)-O(1) bond length is 1.26 Å. The C(1)-O(2) bond length is 1.23 Å. In the seventh C site, C(2) is bonded in a 3-coordinate geometry to one C(3); one N(2); and two equivalent H(13,14) atoms. The C(2)-C(3) bond length is 1.46 Å. The C(2)-N(2) bond length is 1.45 Å. Both C(2)-H(13,14) bond lengths are 0.97 Å. In the eighth C site, C(3) is bonded in a distorted trigonal planar geometry to one C(2), one O(3), and one O(4) atom. The C(3)-O(3) bond length is 1.26 Å. The C(3)-O(4) bond length is 1.24 Å. In the ninth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(4)-O(5) bond length is 1.25 Å. The C(4)-O(6) bond length is 1.23 Å. In the tenth C site, C(5) is bonded in a distorted trigonal non-coplanar geometry to one C(6); one N(4); and two equivalent H(15,16) atoms. The C(5)-C(6) bond length is 1.50 Å. The C(5)-N(4) bond length is 1.42 Å. Both C(5)-H(15,16) bond lengths are 0.97 Å. In the eleventh C site, C(6) is bonded in a distorted trigonal planar geometry to one C(5), one O(7), and one O(8) atom. The C(6)-O(7) bond length is 1.27 Å. The C(6)-O(8) bond length is 1.23 Å. In the twelfth C site, C(7) is bonded in a 3-coordinate geometry to one C(8), one N(5), one H(17), and one H(18) atom. The C(7)-C(8) bond length is 1.50 Å. The C(7)-N(5) bond length is 1.43 Å. The C(7)-H(17) bond length is 0.97 Å. The C(7)-H(18) bond length is 0.97 Å. In the thirteenth C site, C(8) is bonded in a distorted trigonal planar geometry to one C(7), one O(10), and one O(9) atom. The C(8)-O(10) bond length is 1.22 Å. The C(8)-O(9) bond length is 1.28 Å. In the fourteenth C site, C(9) is bonded in a 3-coordinate geometry to one N(6), one H(19), and one H(20) atom. The C(9)-N(6) bond length is 1.45 Å. The C(9)-H(19) bond length is 0.97 Å. The C(9)-H(20) bond length is 0.97 Å. In the fifteenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one O(11) and one O(12) atom. The C(10)-O(11) bond length is 1.29 Å. The C(10)-O(12) bond length is 1.21 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a distorted tetrahedral geometry to one Cu(1), one C(15), one H(1), and one H(2) atom. The N(1)-H(1) bond length is 0.90 Å. The N(1)-H(2) bond length is 0.90 Å. In the second N site, N(2) is bonded in a distorted tetrahedral geometry to one Cu(2), one C(2), one H(3), and one H(4) atom. The N(2)-H(3) bond length is 0.90 Å. The N(2)-H(4) bond length is 0.90 Å. In the third N site, N(3) is bonded in a distorted tetrahedral geometry to one Cu(3), one C(14), one H(5), and one H(6) atom. The N(3)-H(5) bond length is 0.90 Å. The N(3)-H(6) bond length is 0.90 Å. In the fourth N site, N(4) is bonded in a distorted tetrahedral geometry to one Cu(4), one C(5), one H(7), and one H(8) atom. The N(4)-H(7) bond length is 0.90 Å. The N(4)-H(8) bond length is 0.90 Å. In the fifth N site, N(5) is bonded in a distorted tetrahedral geometry to one Cu(5), one C(7), one H(10), and one H(9) atom. The N(5)-H(10) bond length is 0.90 Å. The N(5)-H(9) bond length is 0.90 Å. In the sixth N site, N(6) is bonded in a distorted tetrahedral geometry to one Cu(6), one C(9), one H(11), and one H(12) atom. The N(6)-H(11) bond length is 0.90 Å. The N(6)-H(12) bond length is 0.90 Å. There are twenty-four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(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 N(2) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one N(2) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one N(3) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one N(3) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one N(4) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one N(4) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one N(5) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one N(5) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one N(6) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one N(6) atom. In the thirteenth H site, H(13,14) is bonded in a single-bond geometry to one C(2) atom. In the fourteenth H site, H(15,16) is bonded in a single-bond geometry to one C(5) atom. In the fifteenth H site, H(17) is bonded in a single-bond geometry to one C(7) atom. In the sixteenth H site, H(18) is bonded in a single-bond geometry to one C(7) atom. In the seventeenth H site, H(19) is bonded in a single-bond geometry to one C(9) atom. In the eighteenth H site, H(20) is bonded in a single-bond geometry to one C(9) atom. In the nineteenth H site, H(21) is bonded in a single-bond geometry to one C(11) atom. In the twentieth H site, H(22) is bonded in a single-bond geometry to one C(12) atom. In the twenty-first H site, H(23) is bonded in a single-bond geometry to one C(13) atom. In the twenty-second H site, H(24,25) is bonded in a single-bond geometry to one C(14) atom. In the twenty-third H site, H(26) is bonded in a single-bond geometry to one C(15) atom. In the twenty-fourth H site, H(27) is bonded in a single-bond geometry to one C(15) atom. There are twenty-one inequivalent O sites. In the first O site, O(11) is bonded in a 3-coordinate geometry to one Tb(1), one Cu(6), and one C(10) atom. In the second O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Cu(5) and one C(10) atom. In the third O site, O(13) is bonded in a trigonal non-coplanar geometry to one Tb(1), one Cu(1), and one Cu(4) atom. In the fourth O site, O(15) is bonded in a trigonal non-coplanar geometry to one Tb(1), one Cu(3), and one Cu(6) atom. In the fifth O site, O(16) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(11) atom. In the sixth O site, O(17) is bonded in a bent 150 degrees geometry to one Tb(2) and one C(11) atom. In the seventh O site, O(19) is bonded in a distorted bent 150 degrees geometry to one Tb(2) and one C(12) atom. In the eighth O site, O(20) is bonded in a bent 120 degrees geometry to one Cu(6) and one C(13) atom. In the ninth O site, O(21) is bonded in a 2-coordinate geometry to one Tb(2) and one C(13) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(8) atom. In the eleventh O site, O(8) is bonded in a bent 120 degrees geometry to one Cu(6) and one C(6) atom. In the twelfth O site, O(18) is bonded in a bent 120 degrees geometry to one Cu(5) and one C(12) atom. In the thirteenth O site, O(14) is bonded in a trigonal non-coplanar geometry to one Tb(1), one Cu(2), and one Cu(5) atom. In the fourteenth O site, O(9) is bonded in a 3-coordinate geometry to one Tb(1), one Cu(5), and one C(8) atom. In the fifteenth O site, O(7) is bonded in a 3-coordinate geometry to one Tb(1), one Cu(4), and one C(6) atom. In the sixteenth O site, O(1) is bonded in a 3-coordinate geometry to one Tb(1), one Cu(1), and one C(1) atom. In the seventeenth O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(3) and one C(1) atom. In the eighteenth O site, O(3) is bonded in a 3-coordinate geometry to one Tb(1), one Cu(2), and one C(3) atom. In the nineteenth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(3) atom. In the twentieth O site, O(5) is bonded in a 3-coordinate geometry to one Tb(1), one Cu(3), and one C(4) atom. In the twenty-first O site, O(6) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(4) atom. Linkers: 108 NCC([O])=O. Metal clusters: 36 [Tb] ,108 [Cu]. The MOF has largest included sphere 9.90 A, density 1.30 g/cm3, surface area 2891.35 m2/g, accessible volume 0.56 cm3/g