Detection and Structure of HOON: Microwave Spectroscopy Reveals an O-O Bond Exceeding 1.9 Å

Nitric oxide (NO) reacts with hydroxyl radicals (OH) in the gas phase to produce nitrous acid, HONO, but essentially nothing is known about the isomeric nitrosyl-O-hydroxide (HOON), owing to its perceived instability. We report the detection of gas-phase HOON in a supersonic molecular beam by Fourier transform microwave spectroscopy and a precise determination of its molecular structure by further spectroscopic analysis of its H-2, N-15, and O-18 isotopologs. HOON contains the longest O-O bond in any known molecule (1.9149 +/- 0.0005 angstrom) and appears surprisingly stable, with an abundance roughly 3% that of HONO in our experiments.