The iron-57 Mossbauer spectra of the phases M,Fel -,CI2*yH20 (M = Mn, Co, or Ni ; x = 0.5 or 0.75; y = 4 or 6) are discussed. The temperature dependence of the quadrupole splitting in the manganese material with x = 0.5 is fitted, to derive the crystal-field splittings; the other phases show similar Mossbauer parameters after ageing for three months, which allows development of the hexahydrate phase ( y = 6). A different ground state is found t o fit the data of the manganese material compared with iron(ii) chloride tetrahydrate, and these results are discussed in terms of the increased lattice spacings found in the parent MCI2*yH20 crystals.In Mossbauer studies on iron(r1) chloride hydrates, the results have been explained 2-14 on the basis of the known crystal structure "*'' of FeCl2.4H20. The quadrupole coupling constant, e'qQ, was found to be p ~s i t i v e , ~* ~~' ~ with the principal axis of the electric field gradient tensor being due to the Fe-C1 bonds of the trans-octahedral FeC12(OH2), unitV7We have reported Mossbauer data for the M,Fel -,C12* 4H2O ( M Mn, Co, or Ni; x = 0-0.75) systems.'8 Phases having more than 50% C0C12 were found to contain a site with a quadrupole splitting of 2.65 mm s-' at 298 K, compared with values of 3.00 and 1.55 mm s-' in other samples having <50"/, CoCI,; the intermediate splitting was noted as being due to an FeC12-4H20 or FeC12*6H20 species, but was not further discussed due to lack of a definite assignment.The detailed temperature dependence of the manganese phase reported previously is evaluated here, and its similarity with the prebiously undiscussed cobalt and nickel phases reported.

Für die Rb‐Komplexe wird eine oktaediische Fe(ll)‐Umgebung mit vier Chloriden und zwei cis‐Wassermolekülen erhalten.

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