Density functional theory calculations (DFT) were performed for the spin-crossover system [Fe(btpa)]²⁺ (btpa = N,N,N′,N′-tetrakis(2-pyridylmethyl)-6,6′-bis(aminomethyl)-2,2′-bipyridine), and for the predominantly low-spin [Fe(b(bdpa))]²⁺ complex (in the solid state) (b(bdpa) = N,N′-bis(benzyl)-N,N′-bis(2-pyridylmethyl)-6,6′-bis(aminomethyl)-2,2′-bipyridine). The calculations confirmed that the former complex exhibits two high-spin isomers of the complexes, i.e. with C₁ quasi hepta-coordinated (long-lived isomer) and C₂ hexa-coordinated (short-lived isomer) structures that have been suggested previously based on time-resolved Raman and flash photolysis experiments. Application of B3LYP and B3LYP* functionals together with the CEP-31G basis yielded reasonable estimates of electronic energies (E_el = E_el(HS) −E_el(LS)) for both isomers (calculated E_el of ca. 24 and 31 kJ mol⁻¹ for long- and short-lived HS isomers, respectively, vs. the experimentally determined value of 27.5 kJ mol⁻¹). Further calculations yielded the electronic structure of the low-spin isomer together with lowest lying singlet and triplet excited states of the [Fe(btpa)]²⁺ as well as the energy profile of the C₂↔C₁isomerisation pathway for the high-spin [Fe(btpa)]²⁺ within the framework of the QST (quadratic synchronous transit) approach. The data obtained are discussed in relation to the observed ultrafast intersystem crossing in Fe(II) polypyridine complexes. The importance of ligand strain in relation to the destabilisation of the low-spin isomers is also discussed. In that context, calculations for a further 15 Fe(II) spin-crossover complexes of hexa-coordinating nitrogen-donor ligands have shown that the LS–HS conversion is associated with a release of ligand stress of 95 ±16 kJ mol⁻¹, on average. On the basis of the calculations presented in this paper we propose that octahedral high-spin d-6 isomers are far more elastic regarding the angular distortions (equatorial and meridional strain, i.e. the declination of cis- and trans-L–M–L angle from the regular values of 90 and 180°, respectively) than their low-spin counterparts.