Abstract: | The unprecedented, fully deprotonated form of acetonitrile, the acetonitriletriide anion CCN3−, is experimentally realized for the first time in the stabilizing bulk host framework of the Ba5TaN4]C2N] nitridometalate via a one‐pot synthesis from the elements under moderate conditions (920 K). The molecular structure of this long‐sought acetonitrile derivative is confirmed by X‐ray diffraction, as well as NMR, IR, and Raman spectroscopy. The anion is isoelectronic to the CO2 molecule, and, in contrast to acetonitrile (H3C−C≡N), the electron pairs are shifted towards two double bonds, that is, C=C=N]3−. |