Zn3P2H2(CO3)4 crystallizes in the triclinic P-1 space group. There are six inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(11), one O(16), one O(17), one O(2), and one O(8) atom to form ZnO6 octahedra that share  a cornercorner with one P(2)CO3 tetrahedra, corners with two equivalent P(1)CO3 tetrahedra, and  an edgeedge with one Zn(2)O6 octahedra. The Zn(1)-O(1) bond length is 2.05 Å. The Zn(1)-O(11) bond length is 2.19 Å. The Zn(1)-O(16) bond length is 2.31 Å. The Zn(1)-O(17) bond length is 2.01 Å. The Zn(1)-O(2) bond length is 2.02 Å. The Zn(1)-O(8) bond length is 2.03 Å. In the second Zn site, Zn(2) is bonded to one O(1), one O(22), one O(23), one O(6), one O(7), and one O(8) atom to form ZnO6 octahedra that share  a cornercorner with one P(1)CO3 tetrahedra, corners with two equivalent P(2)CO3 tetrahedra, and  an edgeedge with one Zn(1)O6 octahedra. The Zn(2)-O(1) bond length is 2.04 Å. The Zn(2)-O(22) bond length is 2.30 Å. The Zn(2)-O(23) bond length is 2.03 Å. The Zn(2)-O(6) bond length is 2.19 Å. The Zn(2)-O(7) bond length is 2.02 Å. The Zn(2)-O(8) bond length is 2.05 Å. In the third Zn site, Zn(3) is bonded to one O(13), one O(3), one O(4), and one O(5) atom to form ZnO4 trigonal pyramids that share  a cornercorner with one P(1)CO3 tetrahedra and  a cornercorner with one P(3)CO3 tetrahedra. The Zn(3)-O(13) bond length is 1.95 Å. The Zn(3)-O(3) bond length is 1.93 Å. The Zn(3)-O(4) bond length is 2.10 Å. The Zn(3)-O(5) bond length is 2.14 Å. In the fourth Zn site, Zn(4) is bonded to one O(10), one O(12), one O(19), and one O(9) atom to form ZnO4 trigonal pyramids that share  a cornercorner with one P(2)CO3 tetrahedra and  a cornercorner with one P(4)CO3 tetrahedra. The Zn(4)-O(10) bond length is 2.11 Å. The Zn(4)-O(12) bond length is 2.13 Å. The Zn(4)-O(19) bond length is 1.94 Å. The Zn(4)-O(9) bond length is 1.92 Å. In the fifth Zn site, Zn(5) is bonded in a 6-coordinate geometry to one Zn(6), one O(15), one O(18), one O(20), one O(21), and one O(24) atom. The Zn(5)-Zn(6) bond length is 0.61 Å. The Zn(5)-O(15) bond length is 2.06 Å. The Zn(5)-O(18) bond length is 2.05 Å. The Zn(5)-O(20) bond length is 2.05 Å. The Zn(5)-O(21) bond length is 1.99 Å. The Zn(5)-O(24) bond length is 2.08 Å. In the sixth Zn site, Zn(6) is bonded in a 6-coordinate geometry to one Zn(5), one O(14), one O(15), one O(18), one O(21), and one O(24) atom. The Zn(6)-O(14) bond length is 2.21 Å. The Zn(6)-O(15) bond length is 1.97 Å. The Zn(6)-O(18) bond length is 2.06 Å. The Zn(6)-O(21) bond length is 2.07 Å. The Zn(6)-O(24) bond length is 2.03 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a 2-coordinate geometry to one C(2), one P(1), one H(1), and one O(4) atom. The C(1)-C(2) bond length is 1.52 Å. The C(1)-P(1) bond length is 1.84 Å. The C(1)-H(1) bond length is 0.98 Å. The C(1)-O(4) bond length is 1.42 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one O(5), and one O(6) atom. The C(2)-O(5) bond length is 1.25 Å. The C(2)-O(6) bond length is 1.24 Å. In the third C site, C(3) is bonded in a 2-coordinate geometry to one C(4), one P(2), one H(2), and one O(10) atom. The C(3)-C(4) bond length is 1.52 Å. The C(3)-P(2) bond length is 1.83 Å. The C(3)-H(2) bond length is 0.98 Å. The C(3)-O(10) bond length is 1.41 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one O(11), and one O(12) atom. The C(4)-O(11) bond length is 1.25 Å. The C(4)-O(12) bond length is 1.25 Å. In the fifth C site, C(5) is bonded in a 4-coordinate geometry to one C(6), one P(3), one H(3), and one O(16) atom. The C(5)-C(6) bond length is 1.52 Å. The C(5)-P(3) bond length is 1.83 Å. The C(5)-H(3) bond length is 0.98 Å. The C(5)-O(16) bond length is 1.44 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(17), and one O(18) atom. The C(6)-O(17) bond length is 1.26 Å. The C(6)-O(18) bond length is 1.26 Å. In the seventh C site, C(7) is bonded in a 2-coordinate geometry to one P(4), one H(4), and one O(22) atom. The C(7)-P(4) bond length is 1.85 Å. The C(7)-H(4) bond length is 0.98 Å. The C(7)-O(22) bond length is 1.45 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one O(23) and one O(24) atom. The C(8)-O(23) bond length is 1.25 Å. The C(8)-O(24) bond length is 1.25 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one C(1), one O(1), one O(2), and one O(3) atom to form PCO3 tetrahedra that share  a cornercorner with one Zn(2)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and  a cornercorner with one Zn(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 46-53°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.49 Å. In the second P site, P(2) is bonded to one C(3), one O(7), one O(8), and one O(9) atom to form PCO3 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with two equivalent Zn(2)O6 octahedra, and  a cornercorner with one Zn(4)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 46-53°. The P(2)-O(7) bond length is 1.51 Å. The P(2)-O(8) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.50 Å. In the third P site, P(3) is bonded to one C(5), one O(13), one O(14), and one O(15) atom to form PCO3 tetrahedra that share  a cornercorner with one Zn(3)O4 trigonal pyramid. The P(3)-O(13) bond length is 1.50 Å. The P(3)-O(14) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.50 Å. In the fourth P site, P(4) is bonded to one C(7), one O(19), one O(20), and one O(21) atom to form PCO3 tetrahedra that share  a cornercorner with one Zn(4)O4 trigonal pyramid. The P(4)-O(19) bond length is 1.51 Å. The P(4)-O(20) bond length is 1.53 Å. The P(4)-O(21) bond length is 1.52 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(5) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(7) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Zn(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Zn(3) and one C(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Zn(3) and one C(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Zn(2) and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Zn(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Zn(4) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Zn(4) and one C(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Zn(1) and one C(4) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Zn(4) and one C(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Zn(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Zn(6) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Zn(5), one Zn(6), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a distorted water-like geometry to one Zn(1) and one C(5) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(6) atom. In the eighteenth O site, O(18) is bonded in a distorted single-bond geometry to one Zn(5), one Zn(6), and one C(6) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Zn(4) and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 120 degrees geometry to one Zn(5) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Zn(5), one Zn(6), and one P(4) atom. In the twenty-second O site, O(22) is bonded in a distorted water-like geometry to one Zn(2) and one C(7) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(8) atom. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one Zn(5), one Zn(6), and one C(8) atom. Linkers: 4 [O]C(=O)[C@@H]([O])P([O])([O])=O ,4 [O]C(=O)[C@H]([O])P([O])([O])=O. Metal clusters: 12 [Zn]. The MOF has largest included sphere 4.49 A, density 2.40 g/cm3, surface area 2348.97 m2/g, accessible volume 0.13 cm3/g