Sodium Salts of Substituted Tetracyanocyclopentadienides [C 5 (CN) 4 X] − (X= H, CN, NH 2 , NO 2 ): Substituent Influence on the Crystal Structures of Potential Coordination Polymers.

Metathesis reactions of NaCl with the silver salts of substituted tetracyanocyclopentadienides [C 5 (CN) 4 X] − (X= H, CN, NO 2 , NH 2 ) gives the corresponding sodium salts 1–4 . While 1–3 give polymeric networks, held together by Pi‐stacking as well as multiply bridging polydentate cyanocyclopentadienides and in part hydrogen bonda, the aminotetracyanocyclo‐pentadienide 4 forms only a water‐bridged dinuclear complexes, which are connected only by an intensive hydrogen bond network. Quite surprisingly, only the NO 2 ‐substituent in 3 coordinates to Na+ besides the cyano groups, while the NH 2 group in 4 is only involved in hydrogen bonds.