An 8-fold interpenetrating diamondoid network, [Ni(cyclam)](2)[TCM].2DMF.10H(2)O, has been prepared by the self-assembly of a Ni(II)cyclam macrocyclic complex and sodium tetrakis[4-(carboxyphenyl)oxamethyl] methane in DMF/water. The network shows an unusual [4 + 4] mode of interpenetration, generating 1D channels of effective window size 6.7 Angstrom x 4.7 Angstrom. The network shows flexible behavior: it becomes nonporous on removal of the guest molecules occupying the channels, but the open structure is restored when the desolvated solid is immersed in the mixture of H2O/DMF (1:1, v/v) for 5 min. The desolvated host has different binding capacities for n-butanol, pyridine, and ethanol.