G. Brewer et al., SPIN-CROSSOVER COMPLEXES OF IRON(II) WITH AN N-4 TETRADENTATE SCHIFF-BASE LIGAND, Inorganica Chimica Acta, 232(1-2), 1995, pp. 183-187
Iron(III) complexes of the Schiff base formed from the condensation of
2-aminobenzaldehyde and ethylenediamine, H(2)amben, were prepared by
the reaction of H(2)amben with iron(III) halides in acetone. Fe(amben)
Cl and Fe(amben)Br.H2O exhibit a spin crossover between the T-2 and (6
)A states as shown by magnetic susceptibility measurements, variable t
emperature Mossbauer spectra, and electron spin resonance at 77 K. Str
uctural investigation of this ligand system was carried out on the cop
per(II) and nickel(II) analogues. Cu(amben) and Ni(amben) are both ort
horhombic with space group P2(1)2(1)2(1) (No. 19) and unit cell parame
ters and volume of a = 7.744(2), b = 26.486(7), c = 6.9706(8) Angstrom
, V = 1429.7(8) Angstrom(3) for Cu(amben) and a = 7.651(1), b = 25.993
(5), c = 7.040(1) Angstrom, V = 1400.1(4) Angstrom(3) for Ni(amben). T
he final R values for Cu(amben) (a total of 1515 reflections of which
1246 were classified as observed (I>3.00 sigma(I)) and Ni(amben) (a to
tal of 1483 reflections of which 979 were classified as observed) are
R = 0.059, R(w) = 0.90 and R = 0.065, R(w) = 0.085, respectively. Both
Cu(amben) and Ni(amben) are monomeric and approximately square planar
. The large dihedral angles between the phenyl rings of Cu(amben) (26.
7 degrees) and Ni(amben) (27.4 degrees) may be related to the observat
ion of spin crossover behavior in the iron(III) complexes.