Eu2Zn19C54N72H54(O9Cl2)4 crystallizes in the hexagonal P6_3/mcm space group. Eu(1) is bonded to six equivalent O(3), one Cl(2), and one Cl(3) atom to form corner-sharing EuCl2O6 hexagonal bipyramids. All Eu(1)-O(3) bond lengths are 2.57 Å. The Eu(1)-Cl(2) bond length is 3.10 Å. The Eu(1)-Cl(3) bond length is 3.08 Å. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in an octahedral geometry to one N(4), two equivalent N(5), two equivalent O(2), and one Cl(1) atom. The Zn(1)-N(4) bond length is 2.12 Å. Both Zn(1)-N(5) bond lengths are 2.04 Å. Both Zn(1)-O(2) bond lengths are 2.19 Å. The Zn(1)-Cl(1) bond length is 2.34 Å. In the second Zn site, Zn(2) is bonded in a 5-coordinate geometry to one N(3), two equivalent O(1), and two equivalent O(3) atoms. The Zn(2)-N(3) bond length is 1.97 Å. Both Zn(2)-O(1) bond lengths are 2.11 Å. Both Zn(2)-O(3) bond lengths are 2.05 Å. In the third Zn site, Zn(3) is bonded in an octahedral geometry to two equivalent N(2) and four equivalent N(7) atoms. Both Zn(3)-N(2) bond lengths are 2.24 Å. All Zn(3)-N(7) bond lengths are 2.13 Å. In the fourth Zn site, Zn(4) is bonded in a trigonal non-coplanar geometry to three equivalent N(6) atoms. All Zn(4)-N(6) bond lengths are 1.95 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(5), and one N(6) atom. The C(1)-N(1) bond length is 1.31 Å. The C(1)-N(5) bond length is 1.35 Å. The C(1)-N(6) bond length is 1.36 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(6), one N(7), and one H(4) atom. The C(2)-N(6) bond length is 1.36 Å. The C(2)-N(7) bond length is 1.28 Å. The C(2)-H(4) bond length is 0.93 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one O(2) and one O(3) atom. The C(3)-O(2) bond length is 1.23 Å. The C(3)-O(3) bond length is 1.24 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to two equivalent O(1) atoms. Both C(4)-O(1) bond lengths are 1.23 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one N(2), one N(3), and one N(8) atom. The C(5)-N(2) bond length is 1.32 Å. The C(5)-N(3) bond length is 1.35 Å. The C(5)-N(8) bond length is 1.37 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one N(3), one N(4), and one H(2) atom. The C(6)-N(3) bond length is 1.33 Å. The C(6)-N(4) bond length is 1.35 Å. The C(6)-H(2) bond length is 0.93 Å. There are eight inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one C(1), one H(1), and one H(3) atom. The N(1)-H(1) bond length is 0.86 Å. The N(1)-H(3) bond length is 0.86 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Zn(3), one C(5), and one N(4) atom. The N(2)-N(4) bond length is 1.36 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one Zn(2), one C(5), and one C(6) atom. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Zn(1), one C(6), and one N(2) atom. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Zn(1), one C(1), and one N(7) atom. The N(5)-N(7) bond length is 1.40 Å. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one Zn(4), one C(1), and one C(2) atom. In the seventh N site, N(7) is bonded in a 3-coordinate geometry to one Zn(3), one C(2), and one N(5) atom. In the eighth N site, N(8) is bonded in a trigonal planar geometry to one C(5) and two equivalent H(5,6) atoms. Both N(8)-H(5,6) bond lengths are 0.86 Å. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one N(1) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(2) atom. In the fifth H site, H(5,6) is bonded in a single-bond geometry to one N(8) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to one Zn(2) and one C(4) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Zn(1) and one C(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Eu(1), one Zn(2), and one C(3) atom. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a single-bond geometry to one Zn(1) atom. In the second Cl site, Cl(2) is bonded in a linear geometry to two equivalent Eu(1) atoms. In the third Cl site, Cl(3) is bonded in a linear geometry to two equivalent Eu(1) atoms. Linkers: 18 [O]C(=O)C([O])=O ,5 NC1=[N]=CN=N1 ,2 NC1=NN=C[N]1 ,8 Nc1nncn1[Zn](n1cnnc1N)n1cnnc1N ,1 NC1=NC=N[N]1 ,1 NC1=N[N]C=N1. Metal clusters: 4 [Eu] ,30 [Zn]. The MOF has largest included sphere 4.62 A, density 1.96 g/cm3, surface area 3100.16 m2/g, accessible volume 0.20 cm3/g