alpha-Fe is the precursor of the reactive Fe-IV=O core responsible for methane oxidation in Fe-containing zeolites. To get more insight into the nature and stability of alpha-Fe in different zeolites, the binding of Fe(II) at six-membered-ring cation exchange sites (6MR) in ZSM-5, zeolite beta, and ferrierite was investigated using DFT and multireference ab initio methods (CASSCF/CASPT2). CASPT2 ligand field (LF) excitation energies of all sites were compared with the experimental DR-UV-vis spectra reported by Snyder et al. From this comparison it is concluded that the 16000 cm(-1) band of alpha-Fe, observed in all three zeolites, can uniquely be assigned to a high-spin square-planar (SP) Fe(II) located at a 6MR with an Al-Si-Si-Al sequence, where the Al atoms are positioned opposite in the ring and as close to each other as possible. The stability of such conformations is also confirmed by the binding energies obtained from DFT. The bands at 10000 cm(-1) in the experimental spectra, assigned to spectator Fe(II), are attributed to six-coordinated trigonal-prismatic Fe(II) species, as calculated for the gamma-site in ZSM-5. The entatic effect of the zeolite lattice on the stability of the SP sites was investigated by making use of the unconstrained Fe(II) model complex FeL2 (with L = [Al(OH)(4)](-)). The SP conformer is approximately 2 kcal/mol more stable than the tetrahedral form, indicating that the SP coordination environment of alpha-Fe is not imposed by the zeolite lattice but rather electronically preferred by Fe(II) in the environment of four O ligands. A significant contribution to the stability of the SP conformer is provided by mixing of the doubly occupied 3d(z)(2) orbital with the higher lying 4s.