Three new coordination polymers, [CoCl2(4-pmna)(2)](n) (1), {[Co(NCS)(2)(4-pmna)(2)](.)2Me(2)CO}(n) (2 superset of 2Me(2)CO), and {[Co(4-pmna)(2)(H2O)(2)](NO3)(2)(.)2CH(3)OH}(n) (3 superset of 2H(2)O(.)2MeOH) (4-pmna) N-(pyridin-4-ylmethyl) nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset of 2Me2CO and 3 superset of 2H(2)O(.)2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset of 2H(2)O(.)2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H(2)O(l) + 2MeOH(l) reversible arrow 3 superset of 2H(2)O(.)2MeOH (approximate to 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset of 2H(2)O(.)2MeOH -> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset of 2H(2)O(.)2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.