The unsymmetrically N-substituted N,N′-Ar 2 -N″-R-1,3,5-triazacyclohexanes 1–4 (Ar=ortho- or para-fluorophenyl, R=n- or iso-propyl) can be obtained in good yields from a one-step condensation reaction with excess amine. Solid state structures of 1–4 resemble closely those of their triaryl-substituted analogues. The condensation reaction to 4 was looked at by detailed NMR investigations and revealed that amine/aniline exchange is occurring in solutions containing free aniline even at ambient conditions setting up an equilibrium between all possible symmetrical and unsymmetrical triazacylcohexanes. Selective crystallisation of 4 from the solution drives the reaction to high yields of 4. Complexes 1–4 react readily with CrCl 3 or CrCl 3 (THF) 3 to form the corresponding CrCl 3 complexes. The complexes are insoluble in non-polar solvents and decompose under decomplexation in coordinating solvents.