Synthesis, structure, and magnetic properties of tetranuclear cubane-like and chain-like iron(II) complexes based on the N(4)O pentadentate dinucleating ligand 1,5-bis[(2-pyridylmethyl)amino]pentan-3-ol

The tetranuclear complexes [Fe(4)(pypentO)(pym)(3)(Oac)(NCS)(3)] x 1.5EtOH (1), [Fe(4)(pypentO)(pym)(Oac)(2)(NCS)(2)(MeO)(2)(H(2)O)] x H(2)O (2), [Fe(2)(pypentO)(NCO)(3)](2) (3), and [Fe(2)(pypentO)(N(3))(3)](2) (4) have been prepared, and their structure and magnetic properties have been studied (pypentOH = 1,5-bis[(2-pyridylmethyl)amino]pentan-3-ol, pymH = 2-pyridylmethanol). The X-ray diffraction analysis of 1 (C(43)H(53)N(10)O(7.5)S(3)Fe(4), monoclinic, P2(1)/n, a = 11.6153(17) A, b = 34.391(17) A, c = 14.2150(18) A, beta = 110.88(5) degrees, V = 5305(3) A(3), Z = 4) and 2 (C(31)H(45)N(7)O(10)S(2)Fe(4), monoclinic, C2/c, a = 19.9165(17) A, b = 21.1001(12) A, c = 21.2617(19) A, beta = 104.441(10) degrees, V = 8652.7(12) A(3), Z = 8) showed a Fe(4)O(4) cubane-like arrangement of four iron(II) atoms, four mu(3)-O bridging ligands, one (1) or two (2) syn-syn bridging acetates. The X-ray diffraction analysis of 3 (C(40)H(46)N(14)O(8)Fe(4), monoclinic, P2(1)/c, a = 11.7633(18) A, b = 18.234(3) A, c = 10.4792(16) A, beta = 99.359(18) degrees, V = 2217.7(6) A(3), Z = 2) and 4 (C(34)H(46)N(26)O(2)Fe(4), monoclinic, P2(1)/c, V = 4412.4(10) A(3), a = 23.534(3) A, b = 18.046(2) A, c = 10.4865(16) A, beta = 97.80(2) degrees, Z = 4) showed a zigzag bis-dinuclear arrangement of four iron(II) cations, two mu(2)-O bridging pypentO ligands, four mu(2)-N-cyanato bridging ligands (3) or four end-on azido bridging ligands (4): they are the first examples of cyanato and azido bridged discrete polynuclear ferrous compounds, respectively. The M?ssbauer spectra of 1 are consistent with four different high-spin iron(II) sites in the Fe(4)O(4) cubane-type structure. The M?ssbauer spectra of 3 are consistent with two high-spin iron(II) sites (N(5)O and N(4)O). Below 190 K, the M?ssbauer spectra of 4 are consistent with one N(5)O and two N(4)O high-spin iron(II) sites. The temperature dependence of the magnetic susceptibility was fitted with J(1) approximately 0 cm(-1), J(2) = -1.3 cm(-1), J(3) = 4.6 cm(-1), D = 6.4 cm(-1), and g = 2.21 for 1; J(1) = 2.6 cm(-1), J(2) = 2.5 cm(-1), J(3) = - 5.6 cm(-1), D = 4.5 cm(-1), and g = 2.09 for 2; J(1) = 1.5 cm(-1), J(2) = 0.2 cm(-1), D = - 5.6 cm(-1), D' = 4.5 cm(-1), and g = 2.14 for 3; and J(1) = - 2.6 cm(-1), J(2) = 0.8 cm(-1), D= 6.3 cm(-1), D' = 1.6 cm(-1), and g = 2.18 for 4. The differences in sign among the J(1), J(2), and J(3) super-exchange interactions indicate that the faces including only mu(3)-OR bridges exhibit ferromagnetic interactions. The nature of the ground state in 1-3 is confirmed by simulation of the magnetization curves at 2 and 5 K. In the bis-dinuclear iron(II) compounds 3 and 4, the J(2) interaction resulting from the bridging of two Fe(2)(pypentO)X(3) units through two pseudo-halide anions is ferromagnetic in 3 (X = mu(2)-N-cyanato) and may be either ferro- or antiferromagnetic in 4 (X = end-on azido). The J(1) interaction through the central O(alkoxo) and pseudo-halide bridges inside the dinuclear units is ferromagnetic in 3 (X = mu(2)-N-cyanato) and antiferromagnetic in 4 (X = end-on azido). In agreement with the symmetry of the two Fe(II) sites in complexes 3 and 4, D (pentacoordinated sites) is larger than D' (octahedral sites).