Synthesis, Crystal Structure, and Magnetic Properties of a Ferrimagnetic Layered Compound [NEt4][Mn(5-Cl-salen)]2[Fe(CN)6] (NEt4 = Tetraethylammonium, 5-Cl-salen = N,N′-Ethylenebis((5-chlorosalicylidene)aminato))

Hitoshi Miyasaka, Naohide Matsumoto, Nazzareno Re, Emma Gallo, Carlo Floriani

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Abstract

The discrete trinuclear complex [(NEt4){Mn(H2O)(5-Cl-salen)}2{Fe(CN) 6}]·H2O, 3, and a two-dimensional heterometal assembly [(NEt4){Mn(5-Cl-salen)}2{Fe(CN)6}]n, 4, have been prepared (NEt4 = tetraethylammonium, 5-Cl-salen = N,N′-ethylenebis(5-chlorosalicylidene)aminato) dianion). Compound 4 crystallizes in the monoclinic space group P21/c with cell dimensions of a = 13.104(3) Å, b = 12.861(3) Å, c = 15.526(2) Å, β = 105.98(1)°, Z = 2 and is isostructural to the previously synthesized metamagnetic compound, [K{Mn(3-MeOsalen}2{Fe-(CN)6}·2DMF]n, 5. The structure assumes a two-dimensional network consisting of the cyclic tetramer (-Mn-NC-Fe-CN-)4 as a net unit [with dimensions of Fe-Cl = 1.947(8) Å, Fe-C2 = 1.951(8) Å, Mn-N1 = 2.286(7) Å, Mn-N2 = 2.266(7) Å, Mn-N-C = 154.4(7)°, Mn-N-C = 146.1(7)°]. The magnetic study (magnetic susceptibility vs T, field-cooled magnetization and zero-field cooled magnetization vs T, hysteresis loop and saturation magnetization vs H up to 55 kOe) shows that the compound is a metamagnet with ferrimagnetic layers and antiferromagnetic interlayer interactions, and with a Neel temperature TN = 4.0 K. The distinctly different magnetic properties of 4 and 5 are discussed and correlated with the structural parameters. The magnetic behavior of 3 was represented by the fitting parameters: gMn = 1-98, gFe = 2.01, J = +5.9 cm-1, D = -6.4 cm-1, zJ′ = -0.38 cm-1 on the basis of a trinuclear spin system (SMn hs, SFe, SMn hs) = (2, 1/2, 2) and includes a zero-field splitting term D and an intermolecular interaction term zJ′ within the molecular field approach. The dehydration reaction of 3 in the solid state also leads to 4.

Original languageEnglish
Pages (from-to)670-676
Number of pages7
JournalInorganic chemistry
Volume36
Issue number4
Publication statusPublished - 1997 Feb 12
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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