Dipartimencome dns Chimica, Università deglns Studi della Calabria, 87030 Arcavacata di Rende, Cosenza, Italy, and also Departament de Química Inorgànica, Facultat de Química de la Universitin ~ de València, Avda. Dr. Moliner 50, 46100 Burjassons (València), Sache
publication background Received
7 march 2000Published
online11 January 2001Published
inconcern 1 February 2001
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ns ready and crystal frameworks that 2 oxalato-linked FeII−FeIIi mixed-valence compounds, 2·8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)3·4H2O (2) (bafternoon = 2,2‘-bipyrimidine; ox = oxalate dianion) to be reported here. Complex 1 crystallizes in ns triclinic system, Gap team P1̄, via a = 10.998(2) Å, b = 13.073(3) Å, c = 13.308(3) Å, α = 101.95(2)°, β = 109.20(2)°, γ = 99.89(2)°, and also Z = 1. Complex 2 crystallizes in the monoclinic system, Space team P21/c, with a = 12.609(2) Å, b = 19.670(5) Å, c = 15.843(3) Å, β = 99.46(1)°, and Z = 4. Ns structure that complex 1 is composed that centrosymmetric oxalato-bridged dinuclean high-spin iron(III) 2- anions, tris-chenthusiastic low-spin iron(II) 2+ cations, and lattice cream water molecules. Ns iron atoms to be hexacoordinated: six oxygen atoms (iron(III)) native two bidentate and one bisbidentate oxalacome ligandns and also 6 nitrogen atoms (iron(II)) native 3 bidentate bafternoon groups. The Fe(III)−O(ox) and also Fe(II)−N(bpm) link distances vary in the arrays 1.967(3)−2.099(3) and 1.967(4)−1.995(3) Å, respectively. Ns iron(III)−iron(III) separation throughout ns bridging oxalato ins 5.449(2) Å, whereas the shorcheck intermolecule iron(III)−iron(II) street is 6.841(2) Å. Ns structure that complex 2 consists the neutratogether heterotrinuclear Fe(bpm)3Na(H2O)2Fe(ox)3 systems and also water molecule of crystallization. The tris-chelated low-spen iron(II) (2+) and high-spin iron(III) (3-) reality act as bidentate ligandns (with two bpm-nitrogen and 2 oxalato-oxygen atoms, respectively) towards ns univalent sodium cation, yieldinns the trinuclear (bpm)2Fe(II)−bpm−Na(I)−ox−Fe(III)(ox)2 complex. 2 cis-combination water molecule finish ns distorted octahedratogether bordering that the salt atom. The arrays that the Fe(II)−N(bpm) and also Fe(III)−O(ox) bond distances <1.968(6)−1.993(5) and 1.992(6)−2.024(6) Å, respectively> compare fine through twater tap observed in 1. Ns Na−N(bpm) bond lengths (2.548(7) and 2.677(7) Å) to be much longer than twater tap of Na−O(ox) (2.514(7) and 2.380(7) Å) and Na−O(water) (2.334(15) and 2.356(12) Å). The intramolecular Fe(II)···Fe(III) separati~ above ins 6.763(2) Å, wheretogether ns shortest intermolecular Fe(II)···Fe(II) and also Fe(III)···Fe(III) distances are 8.152(2) and also 8.992(2) Å, respectively. Magnetic susceptibility dimensions in the temperature array 2.0−290 K for 1 disclose that ns high-spen iron(III) ion are antiferromagnetically coupled (J = −6.6 cm-1, ns Hamiltonia gift defined as Ĥ = −JŜ1·Ŝ2). The magnitude the the antiferromagnetic couplinns via ns bridginns oxalato in ns magneto-structurallied defined family the recipe (2m-10)+ (M = Fe(III) (1), Cr(III), and also Ni(II)) is analyzed and also disputed through indicates that a simple orbital model.
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