Zn5P2H8(CO)16 crystallizes in the triclinic P-1 space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted ZnO4 tetrahedra that share  a cornercorner with one P(1)CO3 tetrahedra. The Zn(1)-O(1) bond length is 1.98 Å. The Zn(1)-O(2) bond length is 2.02 Å. The Zn(1)-O(3) bond length is 2.01 Å. The Zn(1)-O(5) bond length is 1.94 Å. In the second Zn site, Zn(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(6), one O(7), and one O(8) atom. The Zn(2)-O(1) bond length is 2.12 Å. The Zn(2)-O(6) bond length is 2.08 Å. The Zn(2)-O(7) bond length is 2.01 Å. The Zn(2)-O(8) bond length is 2.05 Å. In the third Zn site, Zn(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Zn(3)-O(1) bond lengths are 2.06 Å. Both Zn(3)-O(2) bond lengths are 2.09 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one H(1) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-C(4) bond length is 1.40 Å. The C(1)-H(1) bond length is 0.93 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one P(1) atom. The C(2)-C(3) bond length is 1.38 Å. The C(2)-P(1) bond length is 1.81 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(5), and one H(2) atom. The C(3)-C(5) bond length is 1.39 Å. The C(3)-H(2) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(1), one C(7), and one C(8) atom. The C(4)-C(7) bond length is 1.38 Å. The C(4)-C(8) bond length is 1.50 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(3), one C(6), and one C(7) atom. The C(5)-C(6) bond length is 1.50 Å. The C(5)-C(7) bond length is 1.39 Å. In the sixth C site, C(6) is bonded in a bent 120 degrees geometry to one C(5), one O(3), and one O(4) atom. The C(6)-O(3) bond length is 1.27 Å. The C(6)-O(4) bond length is 1.25 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(4), one C(5), and one H(3) atom. The C(7)-H(3) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(5), and one O(6) atom. The C(8)-O(5) bond length is 1.27 Å. The C(8)-O(6) bond length is 1.25 Å. P(1) is bonded to one C(2), one O(2), one O(7), and one O(8) atom to form PCO3 tetrahedra that share  a cornercorner with one Zn(1)O4 tetrahedra. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.52 Å. The P(1)-O(8) bond length is 1.51 Å. There are four 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(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(1) atom. The H(4)-O(1) bond length is 0.88 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Zn(1), one Zn(2), one Zn(3), and one H(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Zn(1), one Zn(3), and one P(1) atom. In the third O site, O(3) is bonded in a water-like geometry to one Zn(1) and one C(6) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one C(6) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(8) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Zn(2) and one C(8) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Zn(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Zn(2) and one P(1) atom. Linkers: 2 [O]C(=O)c1cc(C([O])=O)cc(P([O])([O])=O)c1. Metal clusters: 5 [Zn]. The MOF has largest included sphere 4.49 A, density 2.01 g/cm3, surface area 2912.09 m2/g, accessible volume 0.21 cm3/g