The molecular geometry of 2-nitrotoluene has been determined by gas phase electron diffraction and quantum chemical computations at the MP2/6-31G * and Becke3-Lee-Yang-Parr (B3-LYP)/6-31G * levels of theory. Computed differences in C-C bond lengths were utilized as constraints in the electron diffraction structure analysis. The scaled B3-LYP/6-31G * force field was used to generate the initial set of vibrational amplitudes. The electron diffraction study yielded the following bond lengths (r g ) and bond angles: C 1 -C 2 , 1.405(8) Å; N-O, 1.231(3) Å; C 1 -C 7 , 1.508(8) Å; C-N, 1.490(9) Å; C 7 -C 1 -C 2 , 127.3(7) o ; N-C 2 -C 3 , 113.8(6) o ; C 1 -C 2 -C 3 , 124.2(9) o ; C 6 -C 1 -C 2 , 114.8(6) o ; C 5 -C 6 -C 1 , 123.1(10) o ; O-N-O, 124.9(3) o ; (C-N), 38(1) o . The structural features of the molecule point to steric interactions prevailing between the methyl and nitro groups.