Na 2 C 3 O 2 : The First Crystalline Compound with the Elusive - C≡C-COO - Anion.

By reaction of sodium electride or NaC 2 H with the anhydrous sodium salt of propiolic acid, Na(OOC-C≡C-H), in liquid ammonia crystalline powders of Na 2 C 3 O 2 were obtained. The structure analysis based on synchrotron powder diffraction data revealed that Na 2 C 3 O 2 crystallizes in a monoclinic unit cell (I2/a, Z=4) exhibiting the elusive Y-shaped - C≡C-COO - anion, which is unprecedented in a crystalline compound up to now. IR/Raman and solid-state NMR spectroscopic investigations with assignments supported by DFT-based ab initio calculations confirm this finding. Reaction with sodium electride led to a higher crystallinity of the product, but additionally a by-product apparently due to decomposition and polymerization of Na 2 C 3 O 2 was formed. No such by-product was observed in the reaction with NaC 2 H, which turned out to be a milder metalation route. However, the product of the latter reaction is less crystalline.