(CN3H6)[FeIIFeIII(SO4)3(H2O)3]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice.

A new guanidinium-templated hydrated iron sulfate, [CN3H6][FeIIFeIII(SO4)3(H2O)3] (1), was prepared from strongly acidic aqueous solutions. Its crystal structure is comprised from FeIIIO6 and FeIIO3(H2O)3 octahedra linked by sulfate bridges forming a [FeIIFeII(SO4)3(H2O)3]- 3D framework with a layer-by-layer ordering of ferric and ferrous cations. The structural topology of the framework is related to the anhydrous rhombohedral mikasaite Fe2(SO4)3. The removal of part of the sulfate tetrahedra and the partial replacement of the Fe3+ cations in the [Fe3+2(SO4)3]0 framework by Fe2+ provide a negative charge and allow the incorporation of the protonated organic species in the voids. The compound 1 has been characterized by single-crystal X-ray diffraction, TG and DSC analyses, UV-vis-NIR spectroscopy, magnetic susceptibility, Mössbauer spectroscopy, IR and Raman spectroscopy, and density functional band-structure calculations. The magnetic behavior of 1 shows an interplay of FeII (S = 2) and FeIII (S = 5/2) sublattices that exhibit different types of antiferromagnetic couplings, one FeIII-FeIII (J1 ∼ 6.1 K) and two FeII-FeIII couplings (J2 ∼ 1 K, J3 ∼ 5.9 K) within corrugated honeycomb layers. These ferrimagnetic layers are coupled antiparallel to each other, resulting in an overall antiferromagnetic order below TN = 31 K.

Chemical Vapor Transport Synthesis of Cu(VO)2(AsO4)2 With Two Distinct Spin-1/2 Magnetic Ions.

A new copper vanadyl arsenate, Cu(VO)2(AsO4)2, was synthesized via the chemical vapor transport method. Cu(VO)2(AsO4)2 adopts an original structure type. It is characterized by layers formed by edge-sharing and corner-sharing V-centered octahedra resulting in a unique topology that was hitherto not reported for vanadates. Single CuO6 octahedra connect vanadate layers into a rigid framework. The thermal expansion of the framework studied by the single-crystal HT X-ray diffraction is reported. The magnetic behavior of Cu(VO)2(AsO4)2 shows an interplay of ferromagnetic V4+-V4+ and antiferromagnetic Cu2+-V4+ interactions that result in a ferrimagnetic long-range order below TC = 66 K.