The 200 MHz1H n.m.r. spectrum of 4,4′-bipyridyl dissolved in the nematic liquid crystal, Phase V, has been obtained and analysed. The dipolar couplings are shown to be consistent with rapid rotation about the inter-ring C–C bond, such that only four positions are appreciably populated, each having an inter-ring angle of 29.6 ± 0.01°. This implies that the barrier to rotation V(θ) of the molecule dissolved in the liquid crystal has maxima at 0 (planar) and 90° which are both relatively high, and that V(90°) is greater than V(0°). These conclusions are obtained only if vibrational averaging of the dipolar couplings is carried out.