Gas-solid chemisorption of HCl and adsorption of MeOH/EtOH by nonporous chiral copper(II) coordination complexes 1.MeOH and 1 ''.MeOH occur in a cooperative and dynamic manner to give solvated second sphere adducts 1'.MeOHZ/EtOH. The chemisorption process involves dramatic atomic rearrangements in the crystalline state upon cleavage and formation of H-Cl, N-H, Cu-N, and Cu-Cl coordination and covalent bonds from the gas and solid state, respectively. Using mechanochemistry, the chloride-bridged coordination complex 1 ''.MeOH is selectively produced by means of a dehydrochlorination reaction, but not in solution in which a mixture of 1 ''.MeOH and 1 ''.MeOH is obtained. 1 ''.MeOH also via chemisorption and adsorption can trap HCl and MeOH to give the second sphere adduct 1 ''.MeOH. The adsorption process is confirmed by forming the second sphere adduct 1'.EtOH by exposing both 1 ''.MeOH and 1 ''.MeOH to HCl and ethanol. Quantum-mechanical (QM) calculations specific for solid phases give insights into the relative stabilities of the hybrid metal organic materials involved in the mechanochemical reaction producing selectively 1 ''.MeOH, giving a good agreement with the experimental results.