The crystal structure of the nitridochromium(V) complex [CrN(salen)] (H 2salen = N, N′-bis(salicylidene)ethylenediamine) has been determined. This complex crystallizes in the monoclinic system, space group P2 1/ c, a = 9.575(1), b = 12.322(3), c = 12.999(2) Å, β = 103.57(1)°, V = 1490.8(5) A ̊ 3 , Z = 4; final R2 = 0.059 ( R = 0.054), wR2 = 0.082 ( wR = 0.044) for 1935 observed reflections ( I⩾1.5 σ( l)). The coordination geometry is square pyramidal with an N 2O 2 donor set (L N202) in the basal plane and the nitride ion at the apex. The UV-Vis spectra of the complex have been re-measured in several solvents and exhibited a d-d band maximum around 540 nm ( ϵ ≈200 M −1cm −1). This is the first example of an observed d-d band among the nitridochromium(V) complexes isolated so far. The ESR spectra have been also re-measured in more detail. The ESR parameters have been compared with those of the [CrN(L N4)] complexes and a remarkable nephelauxetic effect of the 3d sub-shell in comparison with the 3s sub-shell is indicated for the nitridochromium(V) complexes.