Synthesis, Structure, and Magnetic Properties of Two New Ferromagnetic/Antiferromagnetic One-Dimensional Nickel(II) Complexes. Magnetostructural Correlations

Two new one-dimensional nickel(II) complexes were synthesized and characterized:  [Ni(N,N-dimethylethylenediamine)(N3)2] (1) and [Ni(2-aminoethylpyridine)(N3)2] (2). The crystal structures of 1 and 2 were solved. Complex
1 crystallizes in the monoclinic system, space group P21/n with a = 10.569(2) Å, b = 7.331(4) Å, c = 12.9072(8) Å, β = 111.324(10)°, and Z = 4. Complex 2 crystallizes in the monoclinic system, space group P21/c with
a = 12.299(5) Å, b = 14.307(2) Å, c = 12.604(3), β = 106.72(2)°, and Z = 4. The two complexes are similar
and may be described as one-dimensional systems with double-azido-bridged ligands in end-to-end and end-on
coordination alternatively. The end-on moiety is almost identical for 1 and 2, but the end-to-end moiety is different
in each structure:  for 1 this part is almost planar but for 2 is nonplanar. In both cases the Ni atoms are situated
in similar distorted octahedral environments. The magnetic properties of the two compounds were studied by
susceptibility measurements vs temperature. The χM vs T plots for 1 and 2 show a global antiferromagnetic behavior
with a maximum near room temperature for 1 and at very low temperature for 2. J values for 1 and 2 were
deduced from the spin Hamiltonian −∑(J1SiSi+1 + J2Si+1Si+2). The computational method was based on the
numerical solution for finite systems of increasing size. J values for 1 were J1 = −187 cm-1 and J2 = +77 cm-1
and for 2 J1 = −28 cm-1 and J2 = +73 cm-1. The positive values correspond to end-on azido ligands and the
negative values to end-to-end azido ligands. Since the geometries of the [Ni(N3)]2 moieties involving the end-on
azido ligands are almost the same in the two structures, the ferromagnetic coupling is nearly identical in the two
compounds, while the significantly different antiferromagnetic couplings reflect the near planarity of the end-to-end Ni2(N3)2 fragment in 1 and its twisted geometry in 2.