An assembly compound [K(18-crown-6)(MeOH)2][Mn(5-Clsalen)(H2O)(MeOH)]2[Fe(CN)6]·4MeOH of isolated metal centers and conversion into a ferrimagnetic compound by desolvation [18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane, 5-Clsalen = N,N′-ethylenebis(5-chlorosalicylideneiminate)]

Abstract

The reaction of [Mn(5-Clsalen)(H₂O)]ClO₄ with [K(18-crown-6)(H₂O)₂]₃[Fe(CN)₆] in methanol gave a double salt, [K(18-crown)(MeOH)₂][Mn(5-Clsalen)(H₂O)(MeOH)]₂[Fe(CN)₆]·4MeOH 1 [5-Clsalen = N,N′-ethylenebis(5-chlorosalicylideneiminate), 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane]. Compound 1 crystallizes in the monoclinic space group C2/c with cell dimensions of a = 29.065(5), b = 14.261(8), c = 18.443(6) Å, β = 98.83(2)°, Z = 4, V = 7553(4) ų. The two [Mn(5-Clsalen)(H₂O)(MeOH)]⁺ cations and the [Fe(CN)₆]^3– anion are hydrogen bonded, through the Mn–OH₂· · ·NC–Fe and Mn–MeOH· · ·NC–Fe linkages, to form a two-dimensional network structure; the O· · ·N separation is 2.768(8) Å in the former linkage and 2.684(8) Å in the latter. The [K(18-crown-6)(MeOH)₂]⁺ cations are situated between the two-dimensional layers. Compound 1 was partially desolvated in air to give [K(18-crown-6)][Mn(5-Clsalen)(H₂O)]₂[Fe(CN)₆] 1′ which exhibited a short range magnetic interaction due to the local formation of magnetically coupled sublattices. Compound 1′ was fully desolvated by heating to 180 °C to give [K(18-crown-6)][Mn(5-Clsalen)]₂[Fe(CN)₆] 2 which exhibited spontaneous magnetization due to the formation of a network extended by Mn–NC–Fe linkages throughout the lattice.