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The single-crystal X-ray structures of dimethyl 2,2′-bipyridine-6,6′-dicarboxylate, C14H12N2O4, and the copper(I) coordination complex bis(dimethyl 2,2′-bipyridine-6,6′-dicarboxylato-κ2N,N′)copper(I) tetrafluoroborate, [Cu(C14H12N2O4)2]BF4, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anticipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter-pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′-bipyridine.