TbH3(CO)6 crystallizes in the triclinic P1 space group. Tb(1,2,3,4) is bonded in a distorted pentagonal pyramidal geometry to one O(1,13); one O(2,14); one O(3,15,21); one O(4,10,22); one O(5,17,23); and one O(6,12,24) atom. The Tb(1,2,3,4)-O(1,13) bond length is 2.44 Å. The Tb(1,2,3,4)-O(2,14) bond length is 2.50 Å. The Tb(1,2,3,4)-O(3,15,21) bond length is 2.27 Å. The Tb(1,2,3,4)-O(4,10,22) bond length is 2.38 Å. The Tb(1,2,3,4)-O(5,17,23) bond length is 2.28 Å. The Tb(1,2,3,4)-O(6,12,24) bond length is 2.36 Å. There are ten inequivalent C sites. In the first C site, C(1,13) is bonded in a bent 120 degrees geometry to one C(2,14); one O(1,13); and one O(2,14) atom. The C(1,13)-C(2,14) bond length is 1.50 Å. The C(1,13)-O(1,13) bond length is 1.25 Å. The C(1,13)-O(2,14) bond length is 1.28 Å. In the second C site, C(2,14) is bonded in a distorted trigonal planar geometry to one C(1,13); one C(2,14); and one H(1,7) atom. The C(2,14)-C(2,14) bond length is 1.31 Å. The C(2,14)-H(1,7) bond length is 1.14 Å. In the third C site, C(3,9,15,21) is bonded in a distorted bent 120 degrees geometry to one C(4,10,16,22); one O(3,15,21); and one O(4,10,22) atom. The C(3,9,15,21)-C(4,10,16,22) bond length is 1.50 Å. The C(3,9,15,21)-O(3,15,21) bond length is 1.25 Å. The C(3,9,15,21)-O(4,10,22) bond length is 1.26 Å. In the fourth C site, C(4,10,16,22) is bonded in a distorted trigonal planar geometry to one C(3,9,15,21); one C(5,11,17,23); and one H(2,5,8,11) atom. The C(4,10,16,22)-C(5,11,17,23) bond length is 1.33 Å. The C(4,10,16,22)-H(2,5,8,11) bond length is 1.14 Å. In the fifth C site, C(5,11,17,23) is bonded in a distorted trigonal planar geometry to one C(4,10,16,22); one C(6,12,18,24); and one H(3,6,9,12) atom. The C(5,11,17,23)-C(6,12,18,24) bond length is 1.49 Å. The C(5,11,17,23)-H(3,6,9,12) bond length is 1.14 Å. In the sixth C site, C(6,12,18,24) is bonded in a bent 120 degrees geometry to one C(5,11,17,23); one O(5,17,23); and one O(6,12,24) atom. The C(6,12,18,24)-O(5,17,23) bond length is 1.26 Å. The C(6,12,18,24)-O(6,12,24) bond length is 1.25 Å. In the seventh C site, C(7) is bonded in a bent 120 degrees geometry to one C(8), one O(7), and one O(8) atom. The C(7)-C(8) bond length is 1.50 Å. The C(7)-O(7) bond length is 1.25 Å. The C(7)-O(8) bond length is 1.28 Å. In the eighth C site, C(8) is bonded in a distorted trigonal planar geometry to one C(20), one C(7), and one H(4) atom. The C(8)-C(20) bond length is 1.31 Å. The C(8)-H(4) bond length is 1.14 Å. In the ninth C site, C(19) is bonded in a bent 120 degrees geometry to one C(20), one O(19), and one O(20) atom. The C(19)-C(20) bond length is 1.50 Å. The C(19)-O(19) bond length is 1.25 Å. The C(19)-O(20) bond length is 1.28 Å. In the tenth C site, C(20) is bonded in a distorted trigonal planar geometry to one C(19), one C(8), and one H(10) atom. The C(20)-H(10) bond length is 1.14 Å. There are five inequivalent H sites. In the first H site, H(1,7) is bonded in a single-bond geometry to one C(2,14) atom. In the second H site, H(2,5,8,11) is bonded in a single-bond geometry to one C(4,10,16,22) atom. In the third H site, H(3,6,9,12) is bonded in a single-bond geometry to one C(5,11,17,23) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(8) atom. In the fifth H site, H(10) is bonded in a single-bond geometry to one C(20) atom. There are fourteen inequivalent O sites. In the first O site, O(1,13) is bonded in a distorted L-shaped geometry to one Tb(1,2,3,4) and one C(1,13) atom. In the second O site, O(2,14) is bonded in a distorted L-shaped geometry to one Tb(1,2,3,4) and one C(1,13) atom. In the third O site, O(3,15,21) is bonded in a linear geometry to one Tb(1,2,3,4) and one C(3,9,15,21) atom. In the fourth O site, O(4,10,22) is bonded in a bent 120 degrees geometry to one Tb(1,2,3,4) and one C(3,9,15,21) atom. In the fifth O site, O(5,17,23) is bonded in a distorted bent 150 degrees geometry to one Tb(1,2,3,4) and one C(6,12,18,24) atom. In the sixth O site, O(6,12,24) is bonded in a distorted bent 150 degrees geometry to one Tb(1,2,3,4) and one C(6,12,18,24) atom. In the seventh O site, O(7) is bonded in a distorted L-shaped geometry to one Tb(1,2,3,4) and one C(7) atom. The O(7)-Tb(1,2,3,4) bond length is 2.44 Å. In the eighth O site, O(8) is bonded in a distorted L-shaped geometry to one Tb(1,2,3,4) and one C(7) atom. The O(8)-Tb(1,2,3,4) bond length is 2.50 Å. In the ninth O site, O(9) is bonded in a linear geometry to one Tb(1,2,3,4) and one C(3,9,15,21) atom. The O(9)-Tb(1,2,3,4) bond length is 2.27 Å. The O(9)-C(3,9,15,21) bond length is 1.25 Å. In the tenth O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Tb(1,2,3,4) and one C(6,12,18,24) atom. The O(11)-Tb(1,2,3,4) bond length is 2.28 Å. The O(11)-C(6,12,18,24) bond length is 1.26 Å. In the eleventh O site, O(16) is bonded in a bent 120 degrees geometry to one Tb(1,2,3,4) and one C(3,9,15,21) atom. The O(16)-Tb(1,2,3,4) bond length is 2.38 Å. The O(16)-C(3,9,15,21) bond length is 1.26 Å. In the twelfth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Tb(1,2,3,4) and one C(6,12,18,24) atom. The O(18)-Tb(1,2,3,4) bond length is 2.36 Å. The O(18)-C(6,12,18,24) bond length is 1.25 Å. In the thirteenth O site, O(19) is bonded in a distorted L-shaped geometry to one Tb(1,2,3,4) and one C(19) atom. The O(19)-Tb(1,2,3,4) bond length is 2.44 Å. In the fourteenth O site, O(20) is bonded in a distorted L-shaped geometry to one Tb(1,2,3,4) and one C(19) atom. The O(20)-Tb(1,2,3,4) bond length is 2.50 Å. Linkers: 6 [O]C(=O)/C=C/C([O])=O. Metal clusters: 4 [Tb]. The MOF has largest included sphere 5.02 A, density 1.64 g/cm3, surface area 2710.84 m2/g, accessible volume 0.27 cm3/g