Mn6C96H48(N8Cl)5 crystallizes in the tetragonal P4/mmm space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in an octahedral geometry to two equivalent N(3), two equivalent N(4), and two equivalent Cl(2) atoms. Both Mn(1)-N(3) bond lengths are 2.00 Å. Both Mn(1)-N(4) bond lengths are 1.99 Å. Both Mn(1)-Cl(2) bond lengths are 2.56 Å. In the second Mn site, Mn(2) is bonded to four equivalent N(2) and one Cl(1) atom to form corner-sharing MnN4Cl square pyramids. All Mn(2)-N(2) bond lengths are 2.23 Å. The Mn(2)-Cl(1) bond length is 2.71 Å. There are ten inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2), one C(8), and one H(1) atom. The C(1)-C(2) bond length is 1.41 Å. The C(1)-C(8) bond length is 1.37 Å. The C(1)-H(1) bond length is 0.93 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(9), and one H(2) atom. The C(2)-C(9) bond length is 1.35 Å. The C(2)-H(2) bond length is 0.93 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(4), one C(6), and one N(3) atom. The C(3)-C(4) bond length is 1.36 Å. The C(3)-C(6) bond length is 1.44 Å. The C(3)-N(3) bond length is 1.39 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(3), one C(5), and one C(8) atom. The C(4)-C(5) bond length is 1.44 Å. The C(4)-C(8) bond length is 1.48 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(4), one C(7), and one N(4) atom. The C(5)-C(7) bond length is 1.41 Å. The C(5)-N(4) bond length is 1.36 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(3) and one H(3) atom. The C(6)-H(3) bond length is 0.93 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(5) and one H(4) atom. The C(7)-H(4) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one C(4) and two equivalent C(1) atoms. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10) and two equivalent C(2) atoms. The C(9)-C(10) bond length is 1.48 Å. In the tenth C site, C(10) is bonded in a distorted trigonal planar geometry to one C(9) and two equivalent N(1) atoms. Both C(10)-N(1) bond lengths are 1.33 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a water-like geometry to one C(10) and one N(2) atom. The N(1)-N(2) bond length is 1.33 Å. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one N(1), and one N(2) atom. The N(2)-N(2) bond length is 1.30 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent C(3) atoms. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent C(5) atoms. 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(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(7) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a square co-planar geometry to four equivalent Mn(2) atoms. In the second Cl site, Cl(2) is bonded in a single-bond geometry to one Mn(1) atom. Linkers: 2 Cl[Mn]123(Cl)[N]4=C5C=CC4=C(c4n2c(C(=C2[N]1=C(C=C2)C(=c1n3c(=C5c2ccc(cc2)C2=NN=N[N]2)cc1)c1ccc(cc1)C1=NN=N[N]1)c1ccc(cc1)C1=NN=N[N]1)cc4)c1ccc(cc1)C1=NN=N[N]1. Metal clusters: 1 Cl[Mn]123N=N[Mn@]4(=N[N][Mn@@]5(=NN=[Mn@@](N=N5)(N=N1)N=N2)N=N4)N=N3. The MOF has largest included sphere 19.11 A, density 0.46 g/cm3, surface area 4220.76 m2/g, accessible volume 1.68 cm3/g