Cyano-bridged homometallic 1-D and bimetallic 2-D assemblies: synthesis, structures, and magnetic properties of [Ni(baepn)(CN)]n(ClO4)n and [Ni(baepn)]2n[Fe(CN)(6)]n(H2O)8n.

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 P21/n with a = 9.560(3) A, b = 10.700(3) A, c = 14.138(9) A, β = 90.18(6)°, and Z = 4; 2 crystallizes in the monoclinic space group P21/c with a = 8.951(2) A, b = 13.672(3) A, c = 14.392(3) A, β = 98.906(4)°, 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 Eg = 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 span...