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The reported compound, {Na 2 [Cu 4 (HCOO) 2 (pa) 4 (CH 3 OH)] · CH 3 OH}  n   ( 1 , H 2 pa = 2-(hydroxyimino)propionic acid), is a sodium salt of an anionic coordination polymer, comprising rare-topology tetranuclear cluster units, linked through Cu–O bonds to form a polymeric chain. Each cluster unit comprises four Cu 2+  cations, chelating 2-(oxyimino)propionate ligands, two formate ligands and one terminal methanol ligand. The neighbouring polymeric chains contact through O–H…O hydrogen bonds and are interconnected by Na–O coordination bonds to form a three-dimensional network.

New rare-topology [Cu 4 ] cluster coordination polymer employing 2-(oxyimino)propionate as a ligand