Complexation of calcium chloride with bis(lactam) ligand L1 allows the formation of both an unstable anhydrous complex, an aqua complex {[Ca₂(μ-L1)₂(H₂O)₉]Cl₄]}_n (1) and a related hydrate incorporating additional lattice water of crystallization {[Ca(μ-L1)(H₂O)₅]Cl₂·H₂O}_n (2). Related mono(lactam) L2 does not form aqua complexes but the anhydrous complex {[CaCl₂(μ-L2)₂]}_n (3), is highly deliquescent. An unusual ethanol solvate is also reported {[CaCl₂(L2)(EtOH)]}_n (4).