Two Polymeric Linear Tri‐nickel(II) Complexes: [Ni 3 (μ 3 ‐dpa) 4 (C 4 O 4 Me)] n (BF 4 ) n and [Ni 3 (μ 3 ‐dpa) 4 (N 3 )] n (PF 6 ) n Synthesis, Structural Characterization and Magnetic Properties

Two new linear tri‐nickel(II) complexes with an infinite polymeric chain, [Ni 3 (μ 3 ‐dpa) 4 (C 4 O 4 Me)](BF 4 ) 1 and [Ni 3 (μ 3 ‐dpa) 4 (N 3 )](PF 6 ) 2 , [dpa − = di(α‐pyridyl)amido anion], have been synthesized and their structures were determined by X‐ray diffraction. Compound 1 crystallizes in the monoclinic system, space group C 2/c, with a = 19.9078(3), b = 13.2986(2), c = 37.6622(5) Å, β = 94.091(1)°, Z = 8. Compound 2 crystallizes in the monoclinic system, space group P 2 1 /n, with a = 13.323(4), b = 23.217(3), c = 17.528(5) Å, β = 94.42(3)°, Z = 4. The two complexes are described as one‐dimensional systems with the (C 4 O 4 Me) − , 1, or N 3 − , 2, serving as a μ‐(1,3) bridged ligand at the two axial sites of each [Ni 3 (μ 3 ‐dpa) 4 ] 2+ fragment. The Ni‐Ni distances of 2.400(1) and 2.402(1) in 1 and 2.389(2), 2.385(2) in 2 are obviously shorter than those of 2.4325(7), 2.4356(7) in the monomeric complex [Ni 3 (μ 3 ‐dpa) 4 (N 3 ) 2 ] 3 . The magnetic properties of complexes 2 and 3 were studied by susceptibility measurements vs temperature. The χ M vs T plots of both complexes show a strong antiferromagnetic behavior. The simulated J 13 values are −95 cm −1 and −97 cm −1 for 2 and 3, respectively.