Syntheses, structures and magnetic properties of the tricyanoethenolate adducts of quadridentate Schiff base manganese (III) complexes

Yoshiki Sato, Hitoshi Miyasaka, Naohide Matsumoto, Hisashi Okawa

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)

Abstract

Manganese (III) complexes [Mn(L1)(NCO)] and [Mn(L2)(NCO)] (H2L1 = N,N1-ethylenebis(3-hydroxy-4-naphthylideneiminate), H2L2 = N,N 1-(1,1,2,2-tetramethylethylene)bis(3-hydroxy-4-naphthylideneiminate)) react with tetracyanoethylene in a mixed solution of dichloromethane and acetonitrile to give the tricyanoethenolate adducts [Mn(L1)(TCEA)(H2O)] (1) and [Mn(L2)(TCEA)] (2) (TCEA = tricyanoethenolate, [(NC)2C=C(CN)O-]), respectively. Compound 1 crystallizes in the triclinic space group P1̄ with a = 10.612(5), b= 13.369(5), c = 9.981(6) Å, α = 108.89(4), β =110.70(4), γ = 77.22(4)°. The Mn(III) assumes an elongated square bipyramidal geometry, in which two apical sites are occupied by an oxygen atom of a water molecule with Mn-O(3) = 2.305(4) Å and by a nitrogen atom of TCEA with Mn-N(3) = 2.390(4) Å. The water oxygen is hydrogen bonded to a nitrogen atom of TCEA of the adjacent molecular unit with O(3)-N(3)* = 3.081(6) Å forming a one-dimensional chain structure of head-to-tail fashion. Compound 2 crystallizes in the monoclinic space group P21/c with a = 14.107(6), b = 12.750(6), c = 16.481(5) Å, β = 103.64(3)°. Compound 2 has a binuclear structure of out-of-plane fashion, where the dimensions of the Mn2O2 core are Mn-Mn* = 3.475(2) Å and Mn-O(1)* = 2.627(3) Å. The Mn(III) assumes a distorted square bipyramidal geometry, in which two apical sites are occupied by the phenoxy oxygen atom of L2 and an oxygen atom of the TCEA anion with 2.163(3) Å. The magnetic susceptibility measurements in the range 4.4-300 K showed that a weak intermolecular antiferromagnetic interaction or/and zero field splitting is operating for 1, while a intradimer ferromagnetic interaction is operating for 2.

Original languageEnglish
Pages (from-to)57-63
Number of pages7
JournalInorganica Chimica Acta
Volume247
Issue number1
DOIs
Publication statusPublished - 1996 Jun 15
Externally publishedYes

Keywords

  • Binuclear complexes
  • Crystal structures
  • Magnetic interaction
  • Manganese complexes
  • One-dimensional complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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