Mn3C8H14(N9O)4 crystallizes in the orthorhombic Ibam space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in an octahedral geometry to four equivalent N(3) and two equivalent O(2) atoms. All Mn(1)-N(3) bond lengths are 2.22 Å. Both Mn(1)-O(2) bond lengths are 2.25 Å. In the second Mn site, Mn(2) is bonded to two equivalent N(1), two equivalent N(9), and two equivalent O(1) atoms to form distorted edge-sharing MnN4O2 octahedra. Both Mn(2)-N(1) bond lengths are 2.48 Å. Both Mn(2)-N(9) bond lengths are 2.30 Å. Both Mn(2)-O(1) bond lengths are 2.06 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(4), and one N(5) atom. The C(1)-N(1) bond length is 1.35 Å. The C(1)-N(4) bond length is 1.34 Å. The C(1)-N(5) bond length is 1.36 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(5), one N(6), and one N(9) atom. The C(2)-N(5) bond length is 1.34 Å. The C(2)-N(6) bond length is 1.35 Å. The C(2)-N(9) bond length is 1.34 Å. There are nine inequivalent N sites. In the first N site, N(5) is bonded in a trigonal planar geometry to one C(1), one C(2), and one H(1) atom. The N(5)-H(1) bond length is 1.05 Å. In the second N site, N(6) is bonded in a 3-coordinate geometry to one C(2), one N(7), and one H(2) atom. The N(6)-N(7) bond length is 1.37 Å. The N(6)-H(2) bond length is 1.02 Å. In the third N site, N(7) is bonded in a water-like geometry to one N(6) and one N(8) atom. The N(7)-N(8) bond length is 1.29 Å. In the fourth N site, N(8) is bonded in a water-like geometry to one N(7) and one N(9) atom. The N(8)-N(9) bond length is 1.37 Å. In the fifth N site, N(9) is bonded in a distorted trigonal planar geometry to one Mn(2), one C(2), and one N(8) atom. In the sixth N site, N(1) is bonded in a 3-coordinate geometry to one Mn(2), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.35 Å. In the seventh N site, N(2) is bonded in a distorted trigonal planar geometry to one N(1), one N(3), and one H(1) atom. The N(2)-N(3) bond length is 1.32 Å. The N(2)-H(1) bond length is 1.78 Å. In the eighth N site, N(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one N(2), and one N(4) atom. The N(3)-N(4) bond length is 1.34 Å. In the ninth N site, N(4) is bonded in a distorted water-like geometry to one C(1) and one N(3) atom. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(2) and one N(5) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(1) atom. The H(3)-O(1) bond length is 0.97 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(2) atom. The H(4)-O(2) bond length is 0.98 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(2) atom. The H(5)-O(2) bond length is 0.97 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Mn(2) and one H(3) atom. In the second O site, O(2) is bonded in a distorted water-like geometry to one Mn(1), one H(4), and one H(5) atom. Linkers: 1 [NH][C]1=N[N]N(N=1)[Mn@@](n1nnc(n1)Nc1[nH]nnn1)(N1[N]N=C([N]1)Nc1[nH]nnn1)N1[N]N=C([N]1)Nc1[nH]nnn1.O.O ,1 O.O.[N]1N=C(Nc2nnn[nH]2)[N]N1[Mn](N1[N]N=C(Nc2nnn[nH]2)[N]1)(N1[N]N=C(Nc2nnn[nH]2)[N]1)n1nnc(Nc2nnn[nH]2)n1 ,1 O.O.[N]1N=C(Nc2nnn[nH]2)[N]N1[Mn](N1[N]N=C(Nc2nnn[nH]2)[N]1)(N1[N]N=C(Nc2nnn[nH]2)[N]1)N1[N]N=C(Nc2nnn[nH]2)[N]1 ,1 O.O.[N][N][C]NC1=N[N]N([Mn](N2[N]N=C(Nc3nnn[nH]3)[N]2)(N2[N]N=C(Nc3nnn[nH]3)[N]2)n2nnc(Nc3nnn[nH]3)n2)[N]1 ,1 O.O.[N][N][C]Nc1nnn([Mn](N2[N]N=C(Nc3nnn[nH]3)[N]2)(N2[N]N=C(Nc3nnn[nH]3)[N]2)n2nnc(Nc3nnn[nH]3)n2)n1 ,1 [NH][C]1=N[N]N(N=1)[Mn@](n1nnc(n1)Nc1[nH]nnn1)(N1[N]N=C([N]1)Nc1[nH]nnn1)N1[N]N=C([N]1)Nc1[nH]nnn1.O.O. Metal clusters: 2 O[Mn].O[Mn]. The MOF has largest included sphere 3.70 A, density 1.97 g/cm3, surface area 3452.33 m2/g, accessible volume 0.12 cm3/g