Tb4Cu13C65N15H48(O4Cl)6 crystallizes in the triclinic P1 space group. There are two inequivalent Tb sites. In the first Tb site, Tb(1,3) is bonded in a 6-coordinate geometry to one H(22,46); one O(10,22); one O(11,23); one O(7,19); one O(8,20); and one O(9,21) atom. The Tb(1,3)-H(22,46) bond length is 2.49 Å. The Tb(1,3)-O(10,22) bond length is 2.30 Å. The Tb(1,3)-O(11,23) bond length is 2.54 Å. The Tb(1,3)-O(7,19) bond length is 2.29 Å. The Tb(1,3)-O(8,20) bond length is 2.36 Å. The Tb(1,3)-O(9,21) bond length is 2.33 Å. In the second Tb site, Tb(2,4) is bonded in a 7-coordinate geometry to one H(24,48); one O(1,13); one O(12,24); one O(2,14); one O(3,15); one O(4,16); and one O(6,18) atom. The Tb(2,4)-H(24,48) bond length is 2.18 Å. The Tb(2,4)-O(1,13) bond length is 2.30 Å. The Tb(2,4)-O(12,24) bond length is 2.43 Å. The Tb(2,4)-O(2,14) bond length is 2.35 Å. The Tb(2,4)-O(3,15) bond length is 2.28 Å. The Tb(2,4)-O(4,16) bond length is 2.34 Å. The Tb(2,4)-O(6,18) bond length is 2.43 Å. There are ten inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one C(33), one N(3), one N(4), and one Cl(1) atom to form distorted CuCN2Cl tetrahedra that share  a cornercorner with one Cu(2)C2NCl tetrahedra and  an edgeedge with one Cu(3)CN3 tetrahedra. The Cu(1)-C(33) bond length is 1.89 Å. The Cu(1)-N(3) bond length is 2.50 Å. The Cu(1)-N(4) bond length is 2.05 Å. The Cu(1)-Cl(1) bond length is 2.33 Å. In the second Cu site, Cu(2) is bonded to one C(1); one C(34); one N(5,12); and one Cl(1) atom to form distorted CuC2NCl tetrahedra that share  a cornercorner with one Cu(1)CN2Cl tetrahedra and  an edgeedge with one Cu(8)C2NCl tetrahedra. The Cu(2)-C(1) bond length is 2.21 Å. The Cu(2)-C(34) bond length is 2.17 Å. The Cu(2)-N(5,12) bond length is 2.04 Å. The Cu(2)-Cl(1) bond length is 2.28 Å. In the third Cu site, Cu(3) is bonded to one C(33), one N(2), one N(3), and one N(6) atom to form distorted edge-sharing CuCN3 tetrahedra. The Cu(3)-C(33) bond length is 2.58 Å. The Cu(3)-N(2) bond length is 2.04 Å. The Cu(3)-N(3) bond length is 1.89 Å. The Cu(3)-N(6) bond length is 2.08 Å. In the fourth Cu site, Cu(4,10) is bonded to one C(2); one N(7,14); and two equivalent Cl(2,5) atoms to form distorted edge-sharing CuCNCl2 tetrahedra. The Cu(4,10)-C(2) bond length is 2.02 Å. The Cu(4,10)-N(7,14) bond length is 2.04 Å. There is one shorter (2.42 Å) and one longer (2.44 Å) Cu(4,10)-Cl(2,5) bond length. In the fifth Cu site, Cu(5,11) is bonded in a 3-coordinate geometry to one C(2); one N(8,15); one Cl(2,5); and one Cl(3,6) atom. The Cu(5,11)-C(2) bond length is 1.94 Å. The Cu(5,11)-N(8,15) bond length is 2.01 Å. The Cu(5,11)-Cl(2,5) bond length is 2.87 Å. The Cu(5,11)-Cl(3,6) bond length is 2.31 Å. In the sixth Cu site, Cu(6,12) is bonded in a 4-coordinate geometry to one Cu(13); one Cl(2,5); and two equivalent Cl(3,6) atoms. The Cu(6,12)-Cu(13) bond length is 1.24 Å. The Cu(6,12)-Cl(2,5) bond length is 2.22 Å. There is one shorter (2.38 Å) and one longer (2.43 Å) Cu(6,12)-Cl(3,6) bond length. In the seventh Cu site, Cu(7) is bonded to one N(1), one N(10), one N(11), and one Cl(4) atom to form distorted CuN3Cl tetrahedra that share  a cornercorner with one Cu(8)C2NCl tetrahedra and  an edgeedge with one Cu(9)N4 tetrahedra. The Cu(7)-N(1) bond length is 1.89 Å. The Cu(7)-N(10) bond length is 2.50 Å. The Cu(7)-N(11) bond length is 2.05 Å. The Cu(7)-Cl(4) bond length is 2.33 Å. In the eighth Cu site, Cu(8) is bonded to one C(1); one C(34); one N(5,12); and one Cl(4) atom to form distorted CuC2NCl tetrahedra that share  a cornercorner with one Cu(7)N3Cl tetrahedra and  an edgeedge with one Cu(2)C2NCl tetrahedra. The Cu(8)-C(1) bond length is 2.17 Å. The Cu(8)-C(34) bond length is 2.21 Å. The Cu(8)-N(5,12) bond length is 2.04 Å. The Cu(8)-Cl(4) bond length is 2.28 Å. In the ninth Cu site, Cu(9) is bonded to one N(1), one N(10), one N(13), and one N(9) atom to form distorted edge-sharing CuN4 tetrahedra. The Cu(9)-N(1) bond length is 2.58 Å. The Cu(9)-N(10) bond length is 1.89 Å. The Cu(9)-N(13) bond length is 2.08 Å. The Cu(9)-N(9) bond length is 2.04 Å. In the tenth Cu site, Cu(13) is bonded in a square co-planar geometry to two equivalent Cu(6,12) and two equivalent Cl(3,6) atoms. Both Cu(13)-Cl(3,6) bond lengths are 2.05 Å. There are thirty-nine inequivalent C sites. In the first C site, C(1) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(8), and one N(2) atom. The C(1)-N(2) bond length is 0.82 Å. In the second C site, C(2) is bonded in a 3-coordinate geometry to one Cu(4,10); one Cu(5,11); and one N(3) atom. The C(2)-N(3) bond length is 1.15 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one N(4) and one H(1,25) atom. The C(3)-N(4) bond length is 1.33 Å. The C(3)-H(1,25) bond length is 0.93 Å. In the fourth C site, C(4,37) is bonded in a distorted single-bond geometry to one C(5,38) and one H(2,26) atom. The C(4,37)-C(5,38) bond length is 1.38 Å. The C(4,37)-H(2,26) bond length is 0.93 Å. In the fifth C site, C(5,38) is bonded in a trigonal planar geometry to one C(4,37); one C(6,39); and one C(8,41) atom. The C(5,38)-C(6,39) bond length is 1.37 Å. The C(5,38)-C(8,41) bond length is 1.52 Å. In the sixth C site, C(6,39) is bonded in a distorted single-bond geometry to one C(5,38) and one H(3,27) atom. The C(6,39)-H(3,27) bond length is 0.93 Å. In the seventh C site, C(7) is bonded in a distorted bent 120 degrees geometry to one N(4) and one H(4,28) atom. The C(7)-N(4) bond length is 1.34 Å. The C(7)-H(4,28) bond length is 0.93 Å. In the eighth C site, C(8,41) is bonded in a distorted bent 120 degrees geometry to one C(5,38); one O(1,13); and one O(2,14) atom. The C(8,41)-O(1,13) bond length is 1.25 Å. The C(8,41)-O(2,14) bond length is 1.25 Å. In the ninth C site, C(9,42) is bonded in a 3-coordinate geometry to one C(10,43); one N(5,12); and one H(5,29) atom. The C(9,42)-C(10,43) bond length is 1.37 Å. The C(9,42)-N(5,12) bond length is 1.32 Å. The C(9,42)-H(5,29) bond length is 0.93 Å. In the tenth C site, C(10,43) is bonded in a distorted single-bond geometry to one C(11,44); one C(9,42); and one H(6,30) atom. The C(10,43)-C(11,44) bond length is 1.37 Å. The C(10,43)-H(6,30) bond length is 0.93 Å. In the eleventh C site, C(11,44) is bonded in a trigonal planar geometry to one C(10,43); one C(12,45); and one C(14,47) atom. The C(11,44)-C(12,45) bond length is 1.39 Å. The C(11,44)-C(14,47) bond length is 1.50 Å. In the twelfth C site, C(12,45) is bonded in a single-bond geometry to one C(11,44); one C(13,46); and one H(7,31) atom. The C(12,45)-C(13,46) bond length is 1.37 Å. The C(12,45)-H(7,31) bond length is 0.93 Å. In the thirteenth C site, C(13,46) is bonded in a 3-coordinate geometry to one C(12,45); one N(5,12); and one H(8,32) atom. The C(13,46)-N(5,12) bond length is 1.34 Å. The C(13,46)-H(8,32) bond length is 0.93 Å. In the fourteenth C site, C(14,47) is bonded in a bent 120 degrees geometry to one C(11,44); one O(3,15); and one O(4,16) atom. The C(14,47)-O(3,15) bond length is 1.25 Å. The C(14,47)-O(4,16) bond length is 1.25 Å. In the fifteenth C site, C(15) is bonded in a 3-coordinate geometry to one C(16,49); one N(6); and one H(9,33) atom. The C(15)-C(16,49) bond length is 1.37 Å. The C(15)-N(6) bond length is 1.34 Å. The C(15)-H(9,33) bond length is 0.93 Å. In the sixteenth C site, C(16,49) is bonded in a distorted single-bond geometry to one C(15); one C(17,50); and one H(10,34) atom. The C(16,49)-C(17,50) bond length is 1.40 Å. The C(16,49)-H(10,34) bond length is 0.93 Å. In the seventeenth C site, C(17,50) is bonded in a trigonal planar geometry to one C(16,49); one C(18,51); and one C(20,53) atom. The C(17,50)-C(18,51) bond length is 1.37 Å. The C(17,50)-C(20,53) bond length is 1.51 Å. In the eighteenth C site, C(18,51) is bonded in a distorted single-bond geometry to one C(17,50) and one H(11,35) atom. The C(18,51)-H(11,35) bond length is 0.93 Å. In the nineteenth C site, C(19) is bonded in a distorted bent 120 degrees geometry to one N(6) and one H(12,36) atom. The C(19)-N(6) bond length is 1.33 Å. The C(19)-H(12,36) bond length is 0.93 Å. In the twentieth C site, C(20,53) is bonded in a distorted bent 120 degrees geometry to one C(17,50); one O(5,17); and one O(6,18) atom. The C(20,53)-O(5,17) bond length is 1.23 Å. The C(20,53)-O(6,18) bond length is 1.27 Å. In the twenty-first C site, C(21,54) is bonded in a distorted bent 120 degrees geometry to one N(7,14) and one H(13,37) atom. The C(21,54)-N(7,14) bond length is 1.32 Å. The C(21,54)-H(13,37) bond length is 0.93 Å. In the twenty-second C site, C(22,55) is bonded in a single-bond geometry to one C(23,56) and one H(14,38) atom. The C(22,55)-C(23,56) bond length is 1.39 Å. The C(22,55)-H(14,38) bond length is 0.93 Å. In the twenty-third C site, C(23,56) is bonded in a trigonal planar geometry to one C(22,55); one C(24,57); and one C(26,59) atom. The C(23,56)-C(24,57) bond length is 1.39 Å. The C(23,56)-C(26,59) bond length is 1.50 Å. In the twenty-fourth C site, C(24,57) is bonded in a distorted single-bond geometry to one C(23,56); one C(25,58); and one H(15,39) atom. The C(24,57)-C(25,58) bond length is 1.37 Å. The C(24,57)-H(15,39) bond length is 0.93 Å. In the twenty-fifth C site, C(25,58) is bonded in a distorted trigonal planar geometry to one C(24,57); one N(7,14); and one H(16,40) atom. The C(25,58)-N(7,14) bond length is 1.34 Å. The C(25,58)-H(16,40) bond length is 0.93 Å. In the twenty-sixth C site, C(26,59) is bonded in a distorted bent 120 degrees geometry to one C(23,56); one O(7,19); and one O(8,20) atom. The C(26,59)-O(7,19) bond length is 1.26 Å. The C(26,59)-O(8,20) bond length is 1.23 Å. In the twenty-seventh C site, C(27,60) is bonded in a distorted bent 120 degrees geometry to one N(8,15) and one H(17,41) atom. The C(27,60)-N(8,15) bond length is 1.31 Å. The C(27,60)-H(17,41) bond length is 0.93 Å. In the twenty-eighth C site, C(28,61) is bonded in a distorted single-bond geometry to one C(29,62) and one H(18,42) atom. The C(28,61)-C(29,62) bond length is 1.39 Å. The C(28,61)-H(18,42) bond length is 0.93 Å. In the twenty-ninth C site, C(29,62) is bonded in a trigonal planar geometry to one C(28,61); one C(30,63); and one C(32,65) atom. The C(29,62)-C(30,63) bond length is 1.37 Å. The C(29,62)-C(32,65) bond length is 1.48 Å. In the thirtieth C site, C(30,63) is bonded in a distorted trigonal planar geometry to one C(29,62); one C(31,64); and one H(19,43) atom. The C(30,63)-C(31,64) bond length is 1.38 Å. The C(30,63)-H(19,43) bond length is 0.93 Å. In the thirty-first C site, C(31,64) is bonded in a distorted bent 120 degrees geometry to one C(30,63); one N(8,15); and one H(20,44) atom. The C(31,64)-N(8,15) bond length is 1.35 Å. The C(31,64)-H(20,44) bond length is 0.93 Å. In the thirty-second C site, C(32,65) is bonded in a bent 120 degrees geometry to one C(29,62); one O(10,22); and one O(9,21) atom. The C(32,65)-O(10,22) bond length is 1.25 Å. The C(32,65)-O(9,21) bond length is 1.26 Å. In the thirty-third C site, C(33) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one N(1) atom. The C(33)-N(1) bond length is 1.15 Å. In the thirty-fourth C site, C(34) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(8), and one N(9) atom. The C(34)-N(9) bond length is 0.82 Å. In the thirty-fifth C site, C(35) is bonded in a 3-coordinate geometry to one Cu(4,10); one Cu(5,11); and one N(10) atom. The C(35)-Cu(4,10) bond length is 2.02 Å. The C(35)-Cu(5,11) bond length is 1.94 Å. The C(35)-N(10) bond length is 1.15 Å. In the thirty-sixth C site, C(36) is bonded in a distorted bent 120 degrees geometry to one N(11) and one H(1,25) atom. The C(36)-N(11) bond length is 1.33 Å. The C(36)-H(1,25) bond length is 0.93 Å. In the thirty-seventh C site, C(40) is bonded in a distorted bent 120 degrees geometry to one N(11) and one H(4,28) atom. The C(40)-N(11) bond length is 1.34 Å. The C(40)-H(4,28) bond length is 0.93 Å. In the thirty-eighth C site, C(48) is bonded in a 3-coordinate geometry to one C(16,49); one N(13); and one H(9,33) atom. The C(48)-C(16,49) bond length is 1.37 Å. The C(48)-N(13) bond length is 1.34 Å. The C(48)-H(9,33) bond length is 0.93 Å. In the thirty-ninth C site, C(52) is bonded in a distorted bent 120 degrees geometry to one N(13) and one H(12,36) atom. The C(52)-N(13) bond length is 1.33 Å. The C(52)-H(12,36) bond length is 0.93 Å. There are twelve inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Cu(7), one Cu(9), and one C(33) atom. In the second N site, N(2) is bonded in a distorted linear geometry to one Cu(3) and one C(1) atom. In the third N site, N(3) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one C(2) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Cu(1), one C(3), and one C(7) atom. In the fifth N site, N(5,12) is bonded in a trigonal planar geometry to one Cu(2); one C(13,46); and one C(9,42) atom. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one Cu(3), one C(15), and one C(19) atom. In the seventh N site, N(7,14) is bonded in a trigonal planar geometry to one Cu(4,10); one C(21,54); and one C(25,58) atom. In the eighth N site, N(8,15) is bonded in a trigonal planar geometry to one Cu(5,11); one C(27,60); and one C(31,64) atom. In the ninth N site, N(9) is bonded in a distorted linear geometry to one Cu(9) and one C(34) atom. In the tenth N site, N(10) is bonded in a 3-coordinate geometry to one Cu(7), one Cu(9), and one C(35) atom. In the eleventh N site, N(11) is bonded in a trigonal planar geometry to one Cu(7), one C(36), and one C(40) atom. In the twelfth N site, N(13) is bonded in a trigonal planar geometry to one Cu(9), one C(48), and one C(52) atom. There are twenty-four inequivalent H sites. In the first H site, H(1,25) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2,26) is bonded in a single-bond geometry to one C(4,37) atom. In the third H site, H(3,27) is bonded in a single-bond geometry to one C(6,39) atom. In the fourth H site, H(4,28) is bonded in a single-bond geometry to one C(7) atom. In the fifth H site, H(5,29) is bonded in a single-bond geometry to one C(9,42) atom. In the sixth H site, H(6,30) is bonded in a single-bond geometry to one C(10,43) atom. In the seventh H site, H(7,31) is bonded in a single-bond geometry to one C(12,45) atom. In the eighth H site, H(8,32) is bonded in a single-bond geometry to one C(13,46) atom. In the ninth H site, H(9,33) is bonded in a single-bond geometry to one C(15) atom. In the tenth H site, H(10,34) is bonded in a single-bond geometry to one C(16,49) atom. In the eleventh H site, H(11,35) is bonded in a single-bond geometry to one C(18,51) atom. In the twelfth H site, H(12,36) is bonded in a single-bond geometry to one C(19) atom. In the thirteenth H site, H(13,37) is bonded in a single-bond geometry to one C(21,54) atom. In the fourteenth H site, H(14,38) is bonded in a single-bond geometry to one C(22,55) atom. In the fifteenth H site, H(15,39) is bonded in a single-bond geometry to one C(24,57) atom. In the sixteenth H site, H(16,40) is bonded in a single-bond geometry to one C(25,58) atom. In the seventeenth H site, H(17,41) is bonded in a single-bond geometry to one C(27,60) atom. In the eighteenth H site, H(18,42) is bonded in a single-bond geometry to one C(28,61) atom. In the nineteenth H site, H(19,43) is bonded in a single-bond geometry to one C(30,63) atom. In the twentieth H site, H(20,44) is bonded in a single-bond geometry to one C(31,64) atom. In the twenty-first H site, H(21,45) is bonded in a single-bond geometry to one O(11,23) atom. The H(21,45)-O(11,23) bond length is 0.85 Å. In the twenty-second H site, H(22,46) is bonded in a single-bond geometry to one Tb(1,3) and one O(11,23) atom. The H(22,46)-O(11,23) bond length is 0.85 Å. In the twenty-third H site, H(23,47) is bonded in a single-bond geometry to one O(12,24) atom. The H(23,47)-O(12,24) bond length is 0.85 Å. In the twenty-fourth H site, H(24,48) is bonded in a single-bond geometry to one Tb(2,4) and one O(12,24) atom. The H(24,48)-O(12,24) bond length is 0.85 Å. There are twelve inequivalent O sites. In the first O site, O(1,13) is bonded in a linear geometry to one Tb(2,4) and one C(8,41) atom. In the second O site, O(2,14) is bonded in a distorted bent 120 degrees geometry to one Tb(2,4) and one C(8,41) atom. In the third O site, O(3,15) is bonded in a linear geometry to one Tb(2,4) and one C(14,47) atom. In the fourth O site, O(4,16) is bonded in a distorted bent 120 degrees geometry to one Tb(2,4) and one C(14,47) atom. In the fifth O site, O(5,17) is bonded in a single-bond geometry to one C(20,53) atom. In the sixth O site, O(6,18) is bonded in a distorted bent 120 degrees geometry to one Tb(2,4) and one C(20,53) atom. In the seventh O site, O(7,19) is bonded in a linear geometry to one Tb(1,3) and one C(26,59) atom. In the eighth O site, O(8,20) is bonded in a distorted bent 120 degrees geometry to one Tb(1,3) and one C(26,59) atom. In the ninth O site, O(9,21) is bonded in a distorted bent 150 degrees geometry to one Tb(1,3) and one C(32,65) atom. In the tenth O site, O(10,22) is bonded in a distorted linear geometry to one Tb(1,3) and one C(32,65) atom. In the eleventh O site, O(11,23) is bonded in a water-like geometry to one Tb(1,3); one H(21,45); and one H(22,46) atom. In the twelfth O site, O(12,24) is bonded in a water-like geometry to one Tb(2,4); one H(23,47); and one H(24,48) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to one Cu(1) and one Cu(2) atom. In the second Cl site, Cl(2,5) is bonded in a 4-coordinate geometry to one Cu(5,11); one Cu(6,12); and two equivalent Cu(4,10) atoms. In the third Cl site, Cl(3,6) is bonded in a 4-coordinate geometry to one Cu(13); one Cu(5,11); and two equivalent Cu(6,12) atoms. In the fourth Cl site, Cl(4) is bonded in a water-like geometry to one Cu(7) and one Cu(8) atom. Linkers: 10 [O]C(=O)c1ccncc1. Metal clusters: 4 [Tb] ,13 [Cu]. The MOF has largest included sphere 5.24 A, density 1.79 g/cm3, surface area 3160.59 m2/g, accessible volume 0.29 cm3/g