Cyano-bridged homometallic 1-d and bimetallic 2-d assemblies: Synthesis, structures, and magnetic properties of [Ni(baepn)(CN)](n)(ClO(4))(n) and [Ni(baepn)](2n)[Fe(CN)(6)](n)(H(2)O)(8n)

Abstract

Cyano-bridged homometallic complex [Ni(baepn)(CN)](n)(ClO4)(n) (1) and bimetallic complex [Ni(baepn)](2n)[Fe(CN)(6)](n)-(H2O)(8n) (2) [baepn = N,N'-bis(2-aminoethyl)-1,3-propanediamine] were synthesized and characterized. 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.560(3) Angstrom, b = 10.700(3) Angstrom, c = 14.138(9) Angstrom, beta = 90.18(6)degrees, and Z = 4; 2 crystallizes in the monoclinic space group P2(1)/c with a = 8.951(2) Angstrom, b = 13.672(3) Angstrom, c = 14.392(3) Angstrom, beta = 98.906(4)degrees, and Z = 4. The complex 1 has one-dimensional structure whose chain vector runs along the b axis with baepn ligands and perchlorate anions alternately arranged up and down in the c direction. The antiferromagnetic nature of 1 was explained in terms of the infinite chain model and Haldane gap, giving g = 2.33, J = -29.4 cm(-1), and the magnitude of Haldane gap E-g = 5.22 K. The complex 2 that constitutes the first example of 2-D bimetallic assembly of Ni(II) ion and ferrocyanide anion is composed of the neutral layers based on the [Ni4Fe4] square grid spanning in the bc plane. For 2, the analysis with the Curie-Weiss law in 2-300 K range results in Theta = 0.200 K and the magnetism was explained in terms of the ability of ferrocyanide in the -Ni-NC-Fe-CN-Ni unit to promote ferromagnetic Ni-Ni interaction.