The molecular structures of 2,6-difluorobenzenamine and 2-fluorobenzenamine have been investigated by gas-phase electron diffraction. The experimental data of the difluoro derivative are consistent with C(s) point group the symmetry plane being perpendicular to the ring and bisecting the H-N-H angle. Considerable angular ring deformation has been found for both molecules, dominated by the presence of the F substituents and consistent with additivity of substituent impact. The structure for the monofluorine derivative, with no symmetry, is less precise than for the difluoro derivative. The ring angles at fluorine and NH2 are 123.6 +/- 0.2-degrees and 115.6 +/- 0.4-degrees for 2,6-difluorobenzenamine and 123.7 +/- 0.8-degrees and 117.6 +/- 1.3-degrees for 2-fluorobenzenamine. The C-F bonds are somewhat tilted toward the amino group, 2.1 +/- 0.5-degrees and 1.3 +/- 0.6-degrees in the difluoro and monofluoro derivatives, respectively. However, there is no other geometrical indication of intramolecular H bond in either molecule. Some further bond lengths (r(g)) and angles with estimated total errors for 2,6-difluorobenzenamine are as follows: N-H 1.009 +/- 0.007 angstrom, (C-C)mean 1.391 +/- 0.003 angstrom, F-C 1.356 +/- 0.004 angstrom, C2C3C4 (gamma) 118.8 +/- 0.2-degrees, C3C4C5 (delta) 119.7 +/- 0.4-degrees, dihedral angle HNH/ring 44 +/- 6-degrees. 2-Fluorobenzenamine: (C-C)mean 1.394 +/- 0.003 angstrom, F-C 1.365 +/- 0.008 angstrom, C1C6C5 (beta') 120.7 +/- 0.9-degrees C2C3C4 (gamma) 118.3 +/- 0.6-degrees, C4C5C6 (gamma') 120.5 +/- 0.6-degrees, C3C4C5 (delta) 119.2 +/- 0.7-degrees, dihedral angle HNH/ring 26 +/- 12-degrees.
