TbC22H(OCl2)6 crystallizes in the orthorhombic Pnna space group. Tb(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Tb(1)-O(2) bond length is 2.33 Å. The Tb(1)-O(3) bond length is 2.46 Å. The Tb(1)-O(4) bond length is 2.42 Å. The Tb(1)-O(5) bond length is 2.39 Å. The Tb(1)-O(6) bond length is 2.41 Å. There are twenty-two inequivalent C sites. In the first C site, C(1) is bonded in a single-bond geometry to one C(16), one C(2), one C(9), and one H(1) atom. The C(1)-C(16) bond length is 1.54 Å. The C(1)-C(2) bond length is 1.48 Å. The C(1)-C(9) bond length is 1.59 Å. The C(1)-H(1) bond length is 0.98 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(7) atom. The C(2)-C(3) bond length is 1.43 Å. The C(2)-C(7) bond length is 1.46 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one Cl(1) atom. The C(3)-C(4) bond length is 1.41 Å. The C(3)-Cl(1) bond length is 1.76 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(3), one C(5), and one Cl(2) atom. The C(4)-C(5) bond length is 1.38 Å. The C(4)-Cl(2) bond length is 1.83 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(4), one C(6), and one C(8) atom. The C(5)-C(6) bond length is 1.42 Å. The C(5)-C(8) bond length is 1.53 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one C(5), one C(7), and one Cl(3) atom. The C(6)-C(7) bond length is 1.46 Å. The C(6)-Cl(3) bond length is 1.78 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(2), one C(6), and one Cl(4) atom. The C(7)-Cl(4) bond length is 1.78 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(1), and one O(4) atom. The C(8)-O(1) bond length is 1.26 Å. The C(8)-O(4) bond length is 1.26 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(1), one C(10), and one C(14) atom. The C(9)-C(10) bond length is 1.45 Å. The C(9)-C(14) bond length is 1.39 Å. In the tenth C site, C(10) is bonded in a trigonal planar geometry to one C(11), one C(9), and one Cl(5) atom. The C(10)-C(11) bond length is 1.42 Å. The C(10)-Cl(5) bond length is 1.77 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one Cl(6) atom. The C(11)-C(12) bond length is 1.41 Å. The C(11)-Cl(6) bond length is 1.73 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one C(11), one C(13), and one C(15) atom. The C(12)-C(13) bond length is 1.42 Å. The C(12)-C(15) bond length is 1.53 Å. In the thirteenth C site, C(13) is bonded in a trigonal planar geometry to one C(12), one C(14), and one Cl(7) atom. The C(13)-C(14) bond length is 1.46 Å. The C(13)-Cl(7) bond length is 1.77 Å. In the fourteenth C site, C(14) is bonded in a distorted trigonal planar geometry to one C(13), one C(9), and one Cl(8) atom. The C(14)-Cl(8) bond length is 1.75 Å. In the fifteenth C site, C(15) is bonded in a distorted bent 120 degrees geometry to one C(12), one O(2), and one O(6) atom. The C(15)-O(2) bond length is 1.26 Å. The C(15)-O(6) bond length is 1.27 Å. In the sixteenth C site, C(16) is bonded in a trigonal planar geometry to one C(1), one C(17), and one C(21) atom. The C(16)-C(17) bond length is 1.41 Å. The C(16)-C(21) bond length is 1.41 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(16), one C(18), and one Cl(9) atom. The C(17)-C(18) bond length is 1.40 Å. The C(17)-Cl(9) bond length is 1.74 Å. In the eighteenth C site, C(18) is bonded in a trigonal planar geometry to one C(17), one C(19), and one Cl(10) atom. The C(18)-C(19) bond length is 1.44 Å. The C(18)-Cl(10) bond length is 1.71 Å. In the nineteenth C site, C(19) is bonded in a trigonal planar geometry to one C(18), one C(20), and one C(22) atom. The C(19)-C(20) bond length is 1.41 Å. The C(19)-C(22) bond length is 1.51 Å. In the twentieth C site, C(20) is bonded in a trigonal planar geometry to one C(19), one C(21), and one Cl(11) atom. The C(20)-C(21) bond length is 1.40 Å. The C(20)-Cl(11) bond length is 1.79 Å. In the twenty-first C site, C(21) is bonded in a trigonal planar geometry to one C(16), one C(20), and one Cl(12) atom. The C(21)-Cl(12) bond length is 1.74 Å. In the twenty-second C site, C(22) is bonded in a distorted bent 120 degrees geometry to one C(19), one O(3), and one O(5) atom. The C(22)-O(3) bond length is 1.26 Å. The C(22)-O(5) bond length is 1.35 Å. H(1) is bonded in a single-bond geometry to one C(1) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one C(8) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Tb(1) and one C(15) atom. In the third O site, O(3) is bonded in a single-bond geometry to one Tb(1) and one C(22) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Tb(1) and one C(8) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Tb(1) and one C(22) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Tb(1) and one C(15) atom. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a single-bond geometry to one C(3) atom. In the second Cl site, Cl(2) is bonded in a single-bond geometry to one C(4) atom. In the third Cl site, Cl(3) is bonded in a single-bond geometry to one C(6) atom. In the fourth Cl site, Cl(4) is bonded in a single-bond geometry to one C(7) atom. In the fifth Cl site, Cl(5) is bonded in a single-bond geometry to one C(10) atom. In the sixth Cl site, Cl(6) is bonded in a single-bond geometry to one C(11) atom. In the seventh Cl site, Cl(7) is bonded in a single-bond geometry to one C(13) atom. In the eighth Cl site, Cl(8) is bonded in a single-bond geometry to one C(14) atom. In the ninth Cl site, Cl(9) is bonded in a single-bond geometry to one C(17) atom. In the tenth Cl site, Cl(10) is bonded in a single-bond geometry to one C(18) atom. In the eleventh Cl site, Cl(11) is bonded in a single-bond geometry to one C(20) atom. In the twelfth Cl site, Cl(12) is bonded in a single-bond geometry to one C(21) atom. Linkers: 5 [O]C(=O)c1c(Cl)c(Cl)c(C(c2c(Cl)c(Cl)c(C([O])=O)c(Cl)c2Cl)c2c(Cl)c(Cl)c(C([O])=O)c(Cl)c2Cl)c(Cl)c1Cl ,3 [O]C(=O)c1c(Cl)c(Cl)c(C(c2c(Cl)c(Cl)c([C]=O)c(Cl)c2Cl)c2c(Cl)c(Cl)c(C([O])=O)c(Cl)c2Cl)c(Cl)c1Cl. Metal clusters: 4 O=[C]O[Tb]123O[C]O[Tb](O[C]=O)(O[C]O1)(O[C]O2)O[C]O3. The MOF has largest included sphere 7.61 A, density 1.19 g/cm3, surface area 3342.80 m2/g, accessible volume 0.51 cm3/g