Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation

Two isostructural heterometallic trinuclear oxalato-bridged complexes of formula C(4)[MCr(2)(ox)(6)(H(2)O)(2)]·nH(2)O (C(+) = 4-aminopyridinium; ox(2-) = oxalate dianion; M(2+) = Mn(2+), n = 3, 1; M(2+) = Co(2+), n = 3.25, 2) have been synthesized by using direct self-assembly methods combining C(3)[Cr(ox)(3)] and the chloride salts of the corresponding metal ion. The crystal structures of both compounds have been resolved by single-crystal X-ray diffraction. They crystallize in the C2/c space group [a = 11.5113(15) Å, b = 20.250(3) Å, c = 21.810(4) Å, beta = 100.447(10) degrees, V = 5161.6(3) Å(3), and Z = 4 for 1, and a = 11.4334(16) Å, b = 20.243(2) Å, c = 21.805(3) Å, beta = 101.113(9) degrees, V = 4951.9(11) Å(3), and Z = 4 for 2]. The structures of 1 and 2 consist of discrete linear [MCr(2)(ox)(6)](4-) bimetallic trinuclear units, pyridinium cations and crystallization water molecules. The linear trinuclear unit is built from a central trans-diaquametal(II), linked to two Cr(ox)(3)](3-) entities by oxalate bridges. One of the oxalate ions is coordinated to the central metal ion whereas the other two oxalate ligands are non-bridging. In the crystal, intermolecular hydrogen bonds involving oxalate ligands, water molecules and pyridinium cations, build a complex three-dimensional network. Variable-temperature magnetic susceptibility measurements for 1 and 2 indicate a weak ferromagnetic interaction (J = +1.16 and +2.62/+2.70 cm(-1) for 1 and 2, respectively) between the two terminal Cr(III) (S(Cr) = 3/2) and the central high-spin Mn(II) (S(Mn) = 5/2) and Co(II) (S(Co) = 3/2) ions. The nature and the amplitude of the exchange interaction are rationalized using DFT calculations and orbital interpretations.