Zn4C9P3H13(NO2)6 crystallizes in the triclinic P-1 space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(1), one N(3), one O(1), and one O(2) atom to form ZnN2O2 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and  a cornercorner with one P(2)O4 tetrahedra. The Zn(1)-N(1) bond length is 1.99 Å. The Zn(1)-N(3) bond length is 1.99 Å. The Zn(1)-O(1) bond length is 2.03 Å. The Zn(1)-O(2) bond length is 1.96 Å. In the second Zn site, Zn(2) is bonded to one N(5), one O(3), one O(4), and one O(5) atom to form ZnNO3 tetrahedra that share  a cornercorner with one Zn(3)O4 tetrahedra,  a cornercorner with one Zn(4)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Zn(2)-N(5) bond length is 1.97 Å. The Zn(2)-O(3) bond length is 2.03 Å. The Zn(2)-O(4) bond length is 2.02 Å. The Zn(2)-O(5) bond length is 1.96 Å. In the third Zn site, Zn(3) is bonded to one O(4), one O(6), one O(7), and one O(8) atom to form ZnO4 tetrahedra that share  a cornercorner with one Zn(2)NO3 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Zn(3)-O(4) bond length is 2.01 Å. The Zn(3)-O(6) bond length is 2.00 Å. The Zn(3)-O(7) bond length is 1.94 Å. The Zn(3)-O(8) bond length is 1.91 Å. In the fourth Zn site, Zn(4) is bonded to one O(10), one O(11), one O(3), and one O(9) atom to form ZnO4 tetrahedra that share  a cornercorner with one Zn(2)NO3 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Zn(4)-O(10) bond length is 1.93 Å. The Zn(4)-O(11) bond length is 1.94 Å. The Zn(4)-O(3) bond length is 2.04 Å. The Zn(4)-O(9) bond length is 1.95 Å. There are nine inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(5) atom. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(2) bond length is 1.35 Å. The C(1)-H(5) bond length is 1.08 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(3), one N(2), and one H(6) atom. The C(2)-C(3) bond length is 1.37 Å. The C(2)-N(2) bond length is 1.38 Å. The C(2)-H(6) bond length is 1.08 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(1), and one H(7) atom. The C(3)-N(1) bond length is 1.39 Å. The C(3)-H(7) bond length is 1.08 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one N(3), one N(4), and one H(8) atom. The C(4)-N(3) bond length is 1.34 Å. The C(4)-N(4) bond length is 1.35 Å. The C(4)-H(8) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one C(6), one N(4), and one H(9) atom. The C(5)-C(6) bond length is 1.37 Å. The C(5)-N(4) bond length is 1.38 Å. The C(5)-H(9) bond length is 1.08 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(5), one N(3), and one H(10) atom. The C(6)-N(3) bond length is 1.39 Å. The C(6)-H(10) bond length is 1.08 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one N(5), one N(6), and one H(11) atom. The C(7)-N(5) bond length is 1.34 Å. The C(7)-N(6) bond length is 1.34 Å. The C(7)-H(11) bond length is 1.08 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(9), one N(6), and one H(12) atom. The C(8)-C(9) bond length is 1.37 Å. The C(8)-N(6) bond length is 1.38 Å. The C(8)-H(12) bond length is 1.08 Å. In the ninth C site, C(9) is bonded in a distorted bent 120 degrees geometry to one C(8), one N(5), and one H(13) atom. The C(9)-N(5) bond length is 1.39 Å. The C(9)-H(13) bond length is 1.08 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)N2O2 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra,  a cornercorner with one Zn(4)O4 tetrahedra, and corners with two equivalent Zn(2)NO3 tetrahedra. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(2), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)N2O2 tetrahedra,  a cornercorner with one Zn(2)NO3 tetrahedra,  a cornercorner with one Zn(4)O4 tetrahedra, and corners with two equivalent Zn(3)O4 tetrahedra. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.59 Å. The P(2)-O(7) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(3)O4 tetrahedra and corners with two equivalent Zn(4)O4 tetrahedra. The P(3)-O(11) bond length is 1.53 Å. The P(3)-O(12) bond length is 1.61 Å. The P(3)-O(8) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.54 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Zn(1), one C(1), and one C(3) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one C(1), one C(2), and one H(2) atom. The N(2)-H(2) bond length is 1.03 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one Zn(1), one C(4), and one C(6) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(4), one C(5), and one H(3) atom. The N(4)-H(3) bond length is 1.04 Å. In the fifth N site, N(5) is bonded in a trigonal planar geometry to one Zn(2), one C(7), and one C(9) atom. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one C(7), one C(8), and one H(4) atom. The N(6)-H(4) bond length is 1.04 Å. There are thirteen inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(12) and one O(5) atom. The H(1)-O(12) bond length is 1.01 Å. The H(1)-O(5) bond length is 1.70 Å. In the second H site, H(2) is bonded in a single-bond geometry to one N(2) atom. In the third H site, H(3) is bonded in a distorted single-bond geometry to one N(4) and one O(6) atom. The H(3)-O(6) bond length is 1.70 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one N(6) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(1) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(2) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(3) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(4) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(5) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(6) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(7) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(8) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(9) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(2) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Zn(2), one Zn(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Zn(2), one Zn(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(2), one P(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(3), one P(1), and one H(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Zn(3) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Zn(4) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Zn(4) and one P(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Zn(4) and one P(3) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one P(3) and one H(1) atom. Linkers: 4 [O]P([O])([O])=O ,2 [O]P([O])(=O)O. Metal clusters: 8 [Zn]. The MOF has largest included sphere 2.31 A, density 2.39 g/cm3, surface area 3227.88 m2/g, accessible volume 0.14 cm3/g