Cyano-Bridged Homometallic 1-D and Bimetallic 2-D Assemblies: Synthesis, Structures, and Magnetic Properties of [Ni(baepn)(CN)]n(C104)n and [Ni(baepn)]2[Fe(CN)6]n(H20)8n

Cyano-bridged homometallic complex [Ni(baepn)(CN)]n(CIC)4)n (1) and bimetallic complex [Ni(baepn)]2n[Fe(CN)e]n(H20)8n (2) [baepn = N,N-bis(2-aminoethyl)-1,3-propanediamine] were synthesized and characterized. 1 crystallizes in the monoclinic space group P2i/n with a = 9.560(3) A, b = 10.700(3) A, c = 14.138(9) A, (beta) = 90.18(6)°, and Z= 4; 2 crystallizes in the monoclinic space group P2i/cwith a = 8.951(2) A, b = 13.672(3) A, c = 14.392(3) , (bete) = 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 , 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(ll) ion and ferrocyanide anion is composed of the neutral layers based on the [Ni4Fe4] square grid spanning in the be plane. For 2, the analysis with the Curie-Weiss law in 2-300 K range results in 0 = 0.200 K and the magnetism was explained in terms of the ability of ferrocyanide in the -Ni-NCFe-CN-Ni unit to promote ferromagnetic Mi-Mi interaction.