Tm2C27NH21O14 crystallizes in the triclinic P-1 space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a distorted pentagonal bipyramidal geometry to one O(1), one O(12), one O(13), one O(25), one O(3), one O(5), and one O(9) atom. The Tm(1)-O(1) bond length is 2.25 Å. The Tm(1)-O(12) bond length is 2.31 Å. The Tm(1)-O(13) bond length is 2.21 Å. The Tm(1)-O(25) bond length is 2.36 Å. The Tm(1)-O(3) bond length is 2.34 Å. The Tm(1)-O(5) bond length is 2.28 Å. The Tm(1)-O(9) bond length is 2.21 Å. In the second Tm site, Tm(2) is bonded in a 7-coordinate geometry to one O(10), one O(14), one O(16), one O(17), one O(21), one O(23), and one O(28) atom. The Tm(2)-O(10) bond length is 2.24 Å. The Tm(2)-O(14) bond length is 2.21 Å. The Tm(2)-O(16) bond length is 2.26 Å. The Tm(2)-O(17) bond length is 2.27 Å. The Tm(2)-O(21) bond length is 2.38 Å. The Tm(2)-O(23) bond length is 2.24 Å. The Tm(2)-O(28) bond length is 2.34 Å. In the third Tm site, Tm(3) is bonded in a distorted pentagonal bipyramidal geometry to one O(15), one O(18), one O(20), one O(22), one O(24), one O(26), and one O(7) atom. The Tm(3)-O(15) bond length is 2.29 Å. The Tm(3)-O(18) bond length is 2.24 Å. The Tm(3)-O(20) bond length is 2.20 Å. The Tm(3)-O(22) bond length is 2.21 Å. The Tm(3)-O(24) bond length is 2.26 Å. The Tm(3)-O(26) bond length is 2.46 Å. The Tm(3)-O(7) bond length is 2.24 Å. In the fourth Tm site, Tm(4) is bonded in a 7-coordinate geometry to one O(11), one O(19), one O(2), one O(27), one O(4), one O(6), and one O(8) atom. The Tm(4)-O(11) bond length is 2.22 Å. The Tm(4)-O(19) bond length is 2.22 Å. The Tm(4)-O(2) bond length is 2.33 Å. The Tm(4)-O(27) bond length is 2.48 Å. The Tm(4)-O(4) bond length is 2.21 Å. The Tm(4)-O(6) bond length is 2.27 Å. The Tm(4)-O(8) bond length is 2.21 Å. There are fifty-four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one H(1), and one O(25) atom. The C(1)-N(1) bond length is 1.34 Å. The C(1)-H(1) bond length is 1.10 Å. The C(1)-O(25) bond length is 1.25 Å. In the second C site, C(2) is bonded in a bent 120 degrees geometry to one C(4), one O(1), and one O(2) atom. The C(2)-C(4) bond length is 1.50 Å. The C(2)-O(1) bond length is 1.27 Å. The C(2)-O(2) bond length is 1.28 Å. In the third C site, C(3) is bonded to one N(2), one H(2), one H(3), and one H(4) atom to form corner-sharing CH3N tetrahedra. The C(3)-N(2) bond length is 1.46 Å. The C(3)-H(2) bond length is 1.10 Å. The C(3)-H(3) bond length is 1.10 Å. The C(3)-H(4) bond length is 1.10 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(12), one C(2), and one C(6) atom. The C(4)-C(12) bond length is 1.40 Å. The C(4)-C(6) bond length is 1.40 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one N(2), one H(5), and one O(28) atom. The C(5)-N(2) bond length is 1.34 Å. The C(5)-H(5) bond length is 1.10 Å. The C(5)-O(28) bond length is 1.25 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(4), one C(7), and one H(6) atom. The C(6)-C(7) bond length is 1.39 Å. The C(6)-H(6) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(6), one C(8), and one H(7) atom. The C(7)-C(8) bond length is 1.40 Å. The C(7)-H(7) bond length is 1.09 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one C(10), one C(11), and one C(7) atom. The C(8)-C(10) bond length is 1.50 Å. The C(8)-C(11) bond length is 1.40 Å. In the ninth C site, C(9) is bonded to one N(2), one H(10), one H(8), and one H(9) atom to form corner-sharing CH3N tetrahedra. The C(9)-N(2) bond length is 1.46 Å. The C(9)-H(10) bond length is 1.10 Å. The C(9)-H(8) bond length is 1.10 Å. The C(9)-H(9) bond length is 1.09 Å. In the tenth C site, C(10) is bonded in a bent 120 degrees geometry to one C(8), one O(3), and one O(4) atom. The C(10)-O(3) bond length is 1.27 Å. The C(10)-O(4) bond length is 1.27 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one C(12), one C(8), and one H(11) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-H(11) bond length is 1.09 Å. In the twelfth C site, C(12) is bonded in a distorted trigonal planar geometry to one C(11), one C(4), and one H(12) atom. The C(12)-H(12) bond length is 1.09 Å. In the thirteenth C site, C(13) is bonded in a bent 120 degrees geometry to one C(14), one O(5), and one O(6) atom. The C(13)-C(14) bond length is 1.50 Å. The C(13)-O(5) bond length is 1.27 Å. The C(13)-O(6) bond length is 1.28 Å. In the fourteenth C site, C(14) is bonded in a trigonal planar geometry to one C(13), one C(15), and one C(20) atom. The C(14)-C(15) bond length is 1.40 Å. The C(14)-C(20) bond length is 1.40 Å. In the fifteenth C site, C(15) is bonded in a distorted trigonal planar geometry to one C(14), one C(16), and one H(13) atom. The C(15)-C(16) bond length is 1.39 Å. The C(15)-H(13) bond length is 1.09 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(14) atom. The C(16)-C(17) bond length is 1.40 Å. The C(16)-H(14) bond length is 1.09 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(16), one C(18), and one C(19) atom. The C(17)-C(18) bond length is 1.50 Å. The C(17)-C(19) bond length is 1.40 Å. In the eighteenth C site, C(18) is bonded in a distorted bent 120 degrees geometry to one C(17), one O(7), and one O(8) atom. The C(18)-O(7) bond length is 1.26 Å. The C(18)-O(8) bond length is 1.28 Å. In the nineteenth C site, C(19) is bonded in a distorted single-bond geometry to one C(17) and one H(15) atom. The C(19)-H(15) bond length is 1.09 Å. In the twentieth C site, C(20) is bonded in a distorted single-bond geometry to one C(14) and one H(16) atom. The C(20)-H(16) bond length is 1.09 Å. In the twenty-first C site, C(21) is bonded in a distorted bent 120 degrees geometry to one C(22), one O(10), and one O(9) atom. The C(21)-C(22) bond length is 1.50 Å. The C(21)-O(10) bond length is 1.26 Å. The C(21)-O(9) bond length is 1.28 Å. In the twenty-second C site, C(22) is bonded in a trigonal planar geometry to one C(21), one C(23), and one C(28) atom. The C(22)-C(23) bond length is 1.40 Å. The C(22)-C(28) bond length is 1.40 Å. In the twenty-third C site, C(23) is bonded in a distorted single-bond geometry to one C(22), one C(24), and one H(17) atom. The C(23)-C(24) bond length is 1.39 Å. The C(23)-H(17) bond length is 1.09 Å. In the twenty-fourth C site, C(24) is bonded in a distorted trigonal planar geometry to one C(23), one C(25), and one H(18) atom. The C(24)-C(25) bond length is 1.41 Å. The C(24)-H(18) bond length is 1.09 Å. In the twenty-fifth C site, C(25) is bonded in a trigonal planar geometry to one C(24), one C(26), and one C(27) atom. The C(25)-C(26) bond length is 1.50 Å. The C(25)-C(27) bond length is 1.40 Å. In the twenty-sixth C site, C(26) is bonded in a distorted bent 120 degrees geometry to one C(25), one O(11), and one O(12) atom. The C(26)-O(11) bond length is 1.28 Å. The C(26)-O(12) bond length is 1.27 Å. In the twenty-seventh C site, C(27) is bonded in a distorted single-bond geometry to one C(25) and one H(19) atom. The C(27)-H(19) bond length is 1.09 Å. In the twenty-eighth C site, C(28) is bonded in a distorted single-bond geometry to one C(22) and one H(20) atom. The C(28)-H(20) bond length is 1.09 Å. In the twenty-ninth C site, C(29) is bonded in a distorted bent 120 degrees geometry to one C(30), one O(13), and one O(14) atom. The C(29)-C(30) bond length is 1.50 Å. The C(29)-O(13) bond length is 1.26 Å. The C(29)-O(14) bond length is 1.27 Å. In the thirtieth C site, C(30) is bonded in a trigonal planar geometry to one C(29), one C(31), and one C(36) atom. The C(30)-C(31) bond length is 1.40 Å. The C(30)-C(36) bond length is 1.40 Å. In the thirty-first C site, C(31) is bonded in a distorted single-bond geometry to one C(30) and one H(21) atom. The C(31)-H(21) bond length is 1.09 Å. In the thirty-second C site, C(32) is bonded in a distorted single-bond geometry to one C(33) and one H(22) atom. The C(32)-C(33) bond length is 1.40 Å. The C(32)-H(22) bond length is 1.09 Å. In the thirty-third C site, C(33) is bonded in a trigonal planar geometry to one C(32), one C(34), and one C(35) atom. The C(33)-C(34) bond length is 1.50 Å. The C(33)-C(35) bond length is 1.40 Å. In the thirty-fourth C site, C(34) is bonded in a bent 120 degrees geometry to one C(33), one O(15), and one O(16) atom. The C(34)-O(15) bond length is 1.28 Å. The C(34)-O(16) bond length is 1.27 Å. In the thirty-fifth C site, C(35) is bonded in a distorted trigonal planar geometry to one C(33), one C(36), and one H(23) atom. The C(35)-C(36) bond length is 1.39 Å. The C(35)-H(23) bond length is 1.09 Å. In the thirty-sixth C site, C(36) is bonded in a distorted single-bond geometry to one C(30), one C(35), and one H(24) atom. The C(36)-H(24) bond length is 1.09 Å. In the thirty-seventh C site, C(37) is bonded in a bent 120 degrees geometry to one C(38), one O(17), and one O(18) atom. The C(37)-C(38) bond length is 1.50 Å. The C(37)-O(17) bond length is 1.27 Å. The C(37)-O(18) bond length is 1.28 Å. In the thirty-eighth C site, C(38) is bonded in a trigonal planar geometry to one C(37), one C(39), and one C(44) atom. The C(38)-C(39) bond length is 1.40 Å. The C(38)-C(44) bond length is 1.40 Å. In the thirty-ninth C site, C(39) is bonded in a distorted single-bond geometry to one C(38) and one H(25) atom. The C(39)-H(25) bond length is 1.09 Å. In the fortieth C site, C(40) is bonded in a distorted single-bond geometry to one C(41) and one H(26) atom. The C(40)-C(41) bond length is 1.40 Å. The C(40)-H(26) bond length is 1.09 Å. In the forty-first C site, C(41) is bonded in a trigonal planar geometry to one C(40), one C(42), and one C(43) atom. The C(41)-C(42) bond length is 1.50 Å. The C(41)-C(43) bond length is 1.40 Å. In the forty-second C site, C(42) is bonded in a distorted bent 120 degrees geometry to one C(41), one O(19), and one O(20) atom. The C(42)-O(19) bond length is 1.26 Å. The C(42)-O(20) bond length is 1.28 Å. In the forty-third C site, C(43) is bonded in a distorted single-bond geometry to one C(41) and one H(27) atom. The C(43)-H(27) bond length is 1.09 Å. In the forty-fourth C site, C(44) is bonded in a distorted single-bond geometry to one C(38) and one H(28) atom. The C(44)-H(28) bond length is 1.09 Å. In the forty-fifth C site, C(45) is bonded in a bent 120 degrees geometry to one C(46), one O(21), and one O(22) atom. The C(45)-C(46) bond length is 1.50 Å. The C(45)-O(21) bond length is 1.27 Å. The C(45)-O(22) bond length is 1.27 Å. In the forty-sixth C site, C(46) is bonded in a trigonal planar geometry to one C(45), one C(47), and one C(48) atom. The C(46)-C(47) bond length is 1.40 Å. The C(46)-C(48) bond length is 1.40 Å. In the forty-seventh C site, C(47) is bonded in a distorted single-bond geometry to one C(46), one C(48), and one H(29) atom. The C(47)-C(48) bond length is 1.39 Å. The C(47)-H(29) bond length is 1.09 Å. In the forty-eighth C site, C(48) is bonded in a distorted trigonal planar geometry to one C(46), one C(47), and one H(30) atom. The C(48)-H(30) bond length is 1.09 Å. In the forty-ninth C site, C(49) is bonded in a bent 120 degrees geometry to one C(50), one O(23), and one O(24) atom. The C(49)-C(50) bond length is 1.50 Å. The C(49)-O(23) bond length is 1.27 Å. The C(49)-O(24) bond length is 1.28 Å. In the fiftieth C site, C(50) is bonded in a trigonal planar geometry to one C(49), one C(51), and one C(52) atom. The C(50)-C(51) bond length is 1.40 Å. The C(50)-C(52) bond length is 1.40 Å. In the fifty-first C site, C(51) is bonded in a distorted trigonal planar geometry to one C(50), one C(52), and one H(31) atom. The C(51)-C(52) bond length is 1.39 Å. The C(51)-H(31) bond length is 1.09 Å. In the fifty-second C site, C(52) is bonded in a distorted trigonal planar geometry to one C(50), one C(51), and one H(32) atom. The C(52)-H(32) bond length is 1.09 Å. In the fifty-third C site, C(53) is bonded to one N(1), one H(37), one H(38), and one H(39) atom to form corner-sharing CH3N tetrahedra. The C(53)-N(1) bond length is 1.45 Å. The C(53)-H(37) bond length is 1.10 Å. The C(53)-H(38) bond length is 1.10 Å. The C(53)-H(39) bond length is 1.10 Å. In the fifty-fourth C site, C(54) is bonded to one N(1), one H(40), one H(41), and one H(42) atom to form corner-sharing CH3N tetrahedra. The C(54)-N(1) bond length is 1.46 Å. The C(54)-H(40) bond length is 1.10 Å. The C(54)-H(41) bond length is 1.10 Å. The C(54)-H(42) bond length is 1.09 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one C(1), one C(53), and one C(54) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one C(3), one C(5), and one C(9) atom. There are forty-two 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(3) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(3) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(5) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(6) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(7) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(9) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(9) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(9) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(11) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(12) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(15) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(16) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(19) 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(23) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(24) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(27) atom. In the twentieth H site, H(20) is bonded in a single-bond geometry to one C(28) atom. In the twenty-first H site, H(21) is bonded in a single-bond geometry to one C(31) atom. In the twenty-second H site, H(22) is bonded in a single-bond geometry to one C(32) atom. In the twenty-third H site, H(23) is bonded in a single-bond geometry to one C(35) atom. In the twenty-fourth H site, H(24) is bonded in a single-bond geometry to one C(36) atom. In the twenty-fifth H site, H(25) is bonded in a single-bond geometry to one C(39) atom. In the twenty-sixth H site, H(26) is bonded in a single-bond geometry to one C(40) atom. In the twenty-seventh H site, H(27) is bonded in a single-bond geometry to one C(43) atom. In the twenty-eighth H site, H(28) is bonded in a single-bond geometry to one C(44) atom. In the twenty-ninth H site, H(29) is bonded in a single-bond geometry to one C(47) atom. In the thirtieth H site, H(30) is bonded in a single-bond geometry to one C(48) atom. In the thirty-first H site, H(31) is bonded in a single-bond geometry to one C(51) atom. In the thirty-second H site, H(32) is bonded in a single-bond geometry to one C(52) atom. In the thirty-third H site, H(33) is bonded in a single-bond geometry to one O(26) atom. The H(33)-O(26) bond length is 0.98 Å. In the thirty-fourth H site, H(34) is bonded in a single-bond geometry to one O(26) atom. The H(34)-O(26) bond length is 0.97 Å. In the thirty-fifth H site, H(35) is bonded in a single-bond geometry to one O(27) atom. The H(35)-O(27) bond length is 0.98 Å. In the thirty-sixth H site, H(36) is bonded in a single-bond geometry to one O(27) atom. The H(36)-O(27) bond length is 0.98 Å. In the thirty-seventh H site, H(37) is bonded in a single-bond geometry to one C(53) atom. In the thirty-eighth H site, H(38) is bonded in a single-bond geometry to one C(53) atom. In the thirty-ninth H site, H(39) is bonded in a single-bond geometry to one C(53) atom. In the fortieth H site, H(40) is bonded in a single-bond geometry to one C(54) atom. In the forty-first H site, H(41) is bonded in a single-bond geometry to one C(54) atom. In the forty-second H site, H(42) is bonded in a single-bond geometry to one C(54) atom. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Tm(1) and one C(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Tm(4) and one C(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Tm(1) and one C(10) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Tm(4) and one C(10) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Tm(1) and one C(13) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Tm(4) and one C(13) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Tm(3) and one C(18) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Tm(4) and one C(18) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Tm(1) and one C(21) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Tm(2) and one C(21) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Tm(4) and one C(26) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Tm(1) and one C(26) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Tm(1) and one C(29) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Tm(2) and one C(29) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Tm(3) and one C(34) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Tm(2) and one C(34) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one Tm(2) and one C(37) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Tm(3) and one C(37) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one Tm(4) and one C(42) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Tm(3) and one C(42) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one Tm(2) and one C(45) atom. In the twenty-second O site, O(22) is bonded in a distorted linear geometry to one Tm(3) and one C(45) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Tm(2) and one C(49) atom. In the twenty-fourth O site, O(24) is bonded in a distorted bent 120 degrees geometry to one Tm(3) and one C(49) atom. In the twenty-fifth O site, O(25) is bonded in a distorted bent 120 degrees geometry to one Tm(1) and one C(1) atom. In the twenty-sixth O site, O(26) is bonded in a distorted water-like geometry to one Tm(3), one H(33), and one H(34) atom. In the twenty-seventh O site, O(27) is bonded in a distorted water-like geometry to one Tm(4), one H(35), and one H(36) atom. In the twenty-eighth O site, O(28) is bonded in a distorted bent 120 degrees geometry to one Tm(2) and one C(5) atom. Linkers: 12 [O]C(=O)c1ccc(C([O])=O)cc1. Metal clusters: 8 [Tm]. The MOF has largest included sphere 6.57 A, density 1.65 g/cm3, surface area 3225.79 m2/g, accessible volume 0.26 cm3/g