Coordination Polymers, IX [1] Synthesis and Crystal Structure of a 1D‐Sodium Coordination Polymer: [NaL 4 (PMDETA)] ∞

Reaction of sodium hydride with the tridentate tetrazole ligand 10 (HL 4 ) and pentamethyldiethylenetriamine (PMDETA) in toluene yields by self‐assembly in the solid‐state the well‐ordered 1D‐coordination polymer [NaL 4 (PMDETA)] ∞ , ( 11 ). The structure of 11 was established by single‐crystal X‐ray diffraction. The generation of the 1D‐polymer 11 is understandable if intermediate formation of coordinatively unsaturated, neutral sodium building blocks [NaL 4 (PMDETA)] ( 12 ) is assumed. Such a self‐complementary monomer 12 acts in a monodentate fashion via its CN group, leading to linkage of monomers and to coordinative saturation at the sodium centre of 12 . The sodium ions of the resulting polymeric chains of 11 are coordinated in a distorted octahedral manner. These results indicate that sodium derivatives of CN‐containing ligands may be tuned as to their dimensionality, especially so since Na + can cope with coordination numbers of 4, 5, or 6, such tuning could be probed initially by provision of further available functionalities within the anionic ligand and/or by provision of Lewis base donors of varying denticity.