Structure of a fluorinated azoxy compound: fluoro(trifluoromethyl)-diazene-2-oxide, CF3N(O)NF.
A gas-phase electron diffraction study of the azoxy compound which was synthesized by the reaction of CF3NO with N2F4 in a Pyrex glass vessel results in a trans CF3N(O)NF structure (F trans to CF3), although quantum chemical calculations (MP2 and B3LYP) predict a greater stability of the cis CF3NN(O)F isomer by about 12 kcal/mol. The CF3 group eclipses the N=N double bond. The following skeletal geometric parameters (r(a) values with 3sigma uncertainties) were obtained: N=N 1.287(15) A; N=O 1.231(6) A; N-F 1.380(6) A; N-C 1.498(6) A; N=N=O 131.2(13) degrees; N=N-F 103.5(13) degrees; N=N-C 114.0(12) degrees. The bond lengths in CF3N(O)NF are compared to those in azo, nitryl, and nitrosyl compounds with fluorine and/or CF3 substituents.
Leibold
Christiane
C
Institut für Physikalische und Theoretische Chemie, Universität Tübingen, 72076 Tübingen, Germany.
Foropoulos
Jerry
J
Marsden
Helen M
HM
Shreeve
Jean'ne M
JM
Oberhammer
Heinz
H