Single crystals of 2D coordination network {Cu 2 L 2 • (DMF) 3 (H 2 O) 3 } n (1-DMF) were prepared by reaction of commercial reagents 3-formyl-4-hydroxybenzoic acid (H 2 L) and Cu(NO 3 ) 2 in dimethylformamide (DMF). The single-crystal structure shows two distinct Cu(II) coordination environments arising from the separate coordination of Cu(II) cations to the carboxylate and salicylaldehydato moieties on the linker, with 1D channels running through the structure. Flexibility is exhibited on solvent exchange with ethanol and tetrahydro-furan, while porosity and the unique overall connectivity of the structure are retained. The activated material exhibits type I gas sorption behaviour and a BET surface area of 950 m 2 g À 1 (N 2 , 77 K). Notably, the framework adsorbs negligible quantities of CH 4 compared with CO 2 and the C 2 H n hydrocarbons. It exhibits exceptional selectivity for C 2 H 2 /CH 4 and C 2 H 2 /C 2 H n , which has applicability in separation technologies for the isolation of C 2 H 2 .[a] M.