RbC6N4H14OI crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 8-coordinate geometry to one N(1), one N(3), two equivalent H(6), two equivalent O(1), and two equivalent I(1) atoms. The Rb(1)-N(1) bond length is 3.14 Å. The Rb(1)-N(3) bond length is 3.28 Å. Both Rb(1)-H(6) bond lengths are 3.07 Å. There is one shorter (2.87 Å) and one longer (2.92 Å) Rb(1)-O(1) bond length. Both Rb(1)-I(1) bond lengths are 3.61 Å. There are four inequivalent C sites. In the first C site, C(2) is bonded to one N(2), one N(3), one H(4), and one H(5) atom to form corner-sharing CH2N2 tetrahedra. The C(2)-N(2) bond length is 1.49 Å. The C(2)-N(3) bond length is 1.47 Å. The C(2)-H(4) bond length is 1.10 Å. The C(2)-H(5) bond length is 1.10 Å. In the second C site, C(3) is bonded to one N(1), one N(3), and two equivalent H(6) atoms to form corner-sharing CH2N2 tetrahedra. The C(3)-N(1) bond length is 1.47 Å. The C(3)-N(3) bond length is 1.47 Å. Both C(3)-H(6) bond lengths are 1.10 Å. In the third C site, C(4) is bonded to two equivalent N(2), one H(7), and one H(8) atom to form corner-sharing CH2N2 tetrahedra. Both C(4)-N(2) bond lengths are 1.48 Å. The C(4)-H(7) bond length is 1.10 Å. The C(4)-H(8) bond length is 1.10 Å. In the fourth C site, C(1) is bonded to one N(1), one N(2), one H(2), and one H(3) atom to form corner-sharing CH2N2 tetrahedra. The C(1)-N(1) bond length is 1.47 Å. The C(1)-N(2) bond length is 1.48 Å. The C(1)-H(2) bond length is 1.10 Å. The C(1)-H(3) bond length is 1.10 Å. There are three inequivalent N sites. In the first N site, N(3) is bonded in a trigonal non-coplanar geometry to one Rb(1), one C(3), and two equivalent C(2) atoms. In the second N site, N(2) is bonded to one C(1), one C(2), one C(4), and one H(1) atom to form distorted corner-sharing NHC3 tetrahedra. The N(2)-H(1) bond length is 1.77 Å. In the third N site, N(1) is bonded in a trigonal non-coplanar geometry to one Rb(1), one C(3), and two equivalent C(1) atoms. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(2) and one O(1) atom. The H(1)-O(1) bond length is 1.01 Å. In the second H site, H(2) is bonded in a single-bond geometry to one C(1) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(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) is bonded in a single-bond geometry to one C(2) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one Rb(1) and one C(3) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(4) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(4) atom. O(1) is bonded in a water-like geometry to two equivalent Rb(1) and two equivalent H(1) atoms. I(1) is bonded in a bent 150 degrees geometry to two equivalent Rb(1) atoms. Linkers: 2 C1N2CN3CN1CN(C2)C3. Metal clusters: 2 [Rb]. The MOF has largest included sphere 2.27 A, density 2.19 g/cm3, surface area 3459.53 m2/g, accessible volume 0.09 cm3/g