The design and synthesis of urea‐based systems suitable for selective anion recognition has demonstrated potential for environmental remediation. These systems act as a double hydrogen‐bond donor to anion acceptors, however, the availability of the carbonyl group to also act as a hydrogen‐bond acceptor has posed as an optimization challenge. One approach to address this obstacle is to design preorganized coordination complexes that decrease the accessibility of the carbonyl group, yet are still capable of anionic hydrogen bonding by secondary coordination. Herein, a new 2‐pyridinylurea ligand, N‐(3‐cyanophenyl)‐N′‐pyridin‐2‐ylurea (L1), and its transition metal complexes, [(L1)2Ni(CH3OH)2](NO3)2, [(L1)2Co(CH3OH)2](NO3)2, [(L1)2Ni(H2O)2](NO3)2 and [(L1)2Cu(ClO4)2]n are reported. Subtle changes in metal‐to‐ligand ratio and solvent conditions yielded dramatically different anion‐binding motifs for two Ni2+ complexes, while bis‐metal coordination of a perchlorate anion in the Cu2+ complex resulted in hydrogen bonding with the weakest available ligand acceptor.