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Hydrated lanthanides picrate complexes with cis-1,3-dithiane-1,3-dioxide (cis-DTSO2). Structure of the Ho compound

2001; Elsevier BV; Volume: 323-324; Linguagem: Inglês

10.1016/s0925-8388(01)01006-4

1873-4669

Paulo B. Miranda, J. Zukerman‐Schpector, P.C. Isolani, G. Vicentini, L.B. Zinner,

Magnetism in coordination complexes

Compounds with composition [Ln(cis-DTSO2)4(H2O)2](pic)3 (pic=picrate, Ln=Pr–Lu and Y) were obtained by reaction of hydrated lanthanide picrate with cis-DTSO2 in absolute ethanol. The adducts were characterized by elemental analyses and IR spectra. The parameters obtained from the absorption spectrum of the solid Nd compound indicate that the metal–ligand bonds present weak covalent character. The low intensity emission spectrum obtained at 77 K for the Eu compound indicates the existence of dimeric species. X-ray powder patterns show only one isomorphous series. X-ray single-crystal data of the holmium compound showed that the crystal system is triclinic, space group P1̄, a=13.387(1) Å, b=14.243(1) Å, c=14.965(1) Å, α=99.879(8)°, β=102.063(9)°, γ=101.620(1). The Ho ion achieves a coordination number of eight by the bonding of two oxygens of one bidentate cis-DTSO2, four oxygens of four monodentate cis-DTSO2, one of which acts as a bridge between two neighboring Ho ions, and two water molecules, giving rise to a distorted square antiprism polyhedron. The picrate anions are not bonded to the Ho(III) ion. The crystal packing is governed by an intricate net of hydrogen bonds.