ZnH3(CO)4 crystallizes in the trigonal R-3 space group. Zn(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted edge-sharing ZnO6 octahedra. The Zn(1)-O(1) bond length is 2.03 Å. The Zn(1)-O(4) bond length is 2.22 Å. There is one shorter (2.18 Å) and one longer (2.37 Å) Zn(1)-O(2) bond length. There is one shorter (2.01 Å) and one longer (2.03 Å) Zn(1)-O(3) bond length. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.49 Å. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(2) bond length is 1.30 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(4) atom. The C(2)-C(3) bond length is 1.40 Å. The C(2)-C(4) bond length is 1.43 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(2), one C(4), and one H(1) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-H(1) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(2), one C(3), and one O(3) atom. The C(4)-O(3) bond length is 1.35 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. The H(2)-O(4) bond length is 0.97 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(4) atom. The H(3)-O(4) bond length is 0.99 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one H(2), and one H(3) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(1) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Zn(1) and one C(1) atom. In the fourth O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one C(4) atom. Linkers: 2 [O][C]c1cc([O])c(C([O])=O)cc1[O] ,3 [O]C(=O)c1cc([O])c(C([O])=O)cc1[O]. Metal clusters: 6 [Zn]. The MOF has largest included sphere 10.37 A, density 1.35 g/cm3, surface area 2524.90 m2/g, accessible volume 0.44 cm3/g