Zn8P6O24Cl crystallizes in the trigonal P-31c space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. The Zn(1)-O(1) bond length is 1.89 Å. The Zn(1)-O(3) bond length is 1.94 Å. There is one shorter (1.99 Å) and one longer (2.00 Å) Zn(1)-O(2) bond length. In the second Zn site, Zn(2) is bonded to three equivalent O(4) and one Cl(1) atom to form distorted ZnClO3 tetrahedra that share  a cornercorner with one Zn(2)ClO3 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. All Zn(2)-O(4) bond lengths are 1.92 Å. The Zn(2)-Cl(1) bond length is 2.39 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(2)ClO3 tetrahedra and corners with four equivalent Zn(1)O4 tetrahedra. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.53 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(4) is bonded in a bent 120 degrees geometry to one Zn(2) and one P(1) atom. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the fourth O site, O(2) is bonded in a trigonal planar geometry to two equivalent Zn(1) and one P(1) atom. Cl(1) is bonded in a linear geometry to two equivalent Zn(2) atoms. Linkers: 12 [O]P([O])([O])=O. Metal clusters: 16 [Zn]. The MOF has largest included sphere 6.48 A, density 2.31 g/cm3, surface area 2293.70 m2/g, accessible volume 0.23 cm3/g