Synthesis, crystal structure and magnetic properties of the alternating chain [VO(H2O)5][Cu2(bipym)2(H2O)(SO4)3]·7H2O (bipym = 2,2′-bipyrimidine)

Abstract

The new compound [VO(H₂O)₅][Cu₂(bipym)₂(H₂O)(SO₄)₃]·7H₂O 1(bipym = 2,2′-bipyrimidine) has been synthesised and its crystal structure determined by single-crystal X-ray diffraction [monoclinic, space group P2₁/c, a= 9.944(3), b= 13.928(6), c= 26.275(6)Å, β= 99.59(2)° and Z= 4]. Its structure consists of anionic alternating zigzag chains of bipym-bridged copper(II) ions with aqua and sulfato ligands. The electroneutrality is achieved by pentaaquaoxovanadium(IV) cations. The coordination geometry around the copper(II) ions can be described as distorted CuN₄O₂ octahedral: that around Cu(1) comprises three nitrogens from bipym and an oxygen from sulfate in the basal positions and a nitrogen from bipym and an oxygen of another sulfate group in the axial sites; three nitrogens from bipym and an oxygen from sulfate occupy the equatorial positions around Cu(2), whereas a nitrogen from bipym and an oxygen from water fill the axial sites. The bipyrimidine group joins two adjacent copper atoms acting in a bis(chelating) fashion. The vanadium atom in the pentaaquavanadyl cation is approximately at the centre of an octahedron defined by five oxygens from water molecules and an oxo group. The V^IV–O (oxo) bond distance [1.577(5) A] is shorter than that of V^IV–O(water)(average 2.025 Å). The intrachain copper–copper separations are 5.505(2) and 5.675(2)Å. Variable-temperature (4.2–300 K) magnetic susceptibility data were fitted by the alternating-chain spin-exchange model [Ĥ=–J∑(Ŝ_2i·Ŝ_2i–1+αŜ_2i·Ŝ_2i+1), α= alternation parameter] and to the usual Bleaney–Bowers expression for a copper(II) pair with the inclusion in both cases of the Curie law for an isolated S=½ species in order to account for the presence of the vanadyl cation. The values of the exchange coupling are discussed in the light of the structural data and compared to those reported for other bipym-bridged copper(II) complexes.