ZnHPO4 crystallizes in the orthorhombic Pbcn 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(4) atom to form ZnO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Zn(1)-O(1) bond length is 1.97 Å. The Zn(1)-O(2) bond length is 1.91 Å. The Zn(1)-O(3) bond length is 1.95 Å. The Zn(1)-O(4) bond length is 1.93 Å. In the second Zn site, Zn(2) is bonded in a 5-coordinate geometry to one Zn(3), one O(11), one O(6), one O(8), and one O(9) atom. The Zn(2)-Zn(3) bond length is 1.32 Å. The Zn(2)-O(11) bond length is 1.93 Å. The Zn(2)-O(6) bond length is 1.98 Å. The Zn(2)-O(8) bond length is 1.89 Å. The Zn(2)-O(9) bond length is 1.95 Å. In the third Zn site, Zn(3) is bonded to one Zn(2), one O(11), one O(8), and one O(9) atom to form distorted ZnZnO3 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Zn(3)-O(11) bond length is 1.95 Å. The Zn(3)-O(8) bond length is 1.92 Å. The Zn(3)-O(9) bond length is 1.96 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(3)ZnO3 tetrahedra and corners with two equivalent Zn(1)O4 tetrahedra. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(7) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Zn(3)ZnO3 tetrahedra. The P(2)-O(10) bond length is 1.52 Å. The P(2)-O(11) bond length is 1.48 Å. The P(2)-O(12) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.48 Å. In the third P site, P(3) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra. Both P(3)-O(1) bond lengths are 1.50 Å. Both P(3)-O(5) bond lengths are 1.54 Å. In the fourth P site, P(4) is bonded to two equivalent O(2) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra. Both P(4)-O(2) bond lengths are 1.49 Å. Both P(4)-O(6) bond lengths are 1.53 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(10) and one O(5) atom. The H(1)-O(10) bond length is 1.63 Å. The H(1)-O(5) bond length is 0.82 Å. In the second H site, H(2) is bonded in a distorted single-bond geometry to one O(10) and one O(7) atom. The H(2)-O(10) bond length is 1.72 Å. The H(2)-O(7) bond length is 0.82 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(12) atom. The H(3)-O(12) bond length is 0.82 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(4) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one P(3) and one H(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(2) and one P(4) atom. In the seventh O site, O(7) is bonded in a water-like geometry to one P(1) and one H(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Zn(2), one Zn(3), and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Zn(2), one Zn(3), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one P(2), one H(1), and one H(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Zn(2), one Zn(3), and one P(2) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one P(2) and one H(3) atom. Linkers: 4 [O]P(=O)(O)O ,4 [O]P([O])([O])=O ,16 [O]P([O])(=O)O. Metal clusters: 24 [Zn]. The MOF has largest included sphere 5.49 A, density 2.05 g/cm3, surface area 2663.13 m2/g, accessible volume 0.21 cm3/g