Synthesis and characterization of [M(DMSO)6][SnCl6] complexes (M = Fe2+, Co2+, and Ni2+) — An old mystery solved

Abstract

The synthesis of an "unknown" Fe(II) complex originally reported in 1973 and formulated then as [Fe(DMSO)5Cl][SnCl4] was thoroughly reproduced and the compound reformulated as the novel [Fe(DMSO)6][SnCl6] double complex salt. Current elemental analysis and IR and Mössbauer spectroscopy matched the original 1973 data, and Raman spectroscopy and single crystal X-ray diffraction provided additional confirmation of our reformulation. [Fe(DMSO)6][SnCl6] (1) crystallizes in the trigonal space group R[Formula: see text] with octahedral [Fe(DMSO)6]2+ and [SnCl6]2– complex ions with an Fe—O bond length of 2.121(3) Å. The same synthesis was extended to Co(II) and Ni(II) to generate the novel [Co(DMSO)6][SnCl6] (2), which crystallizes in the triclinic space group P[Formula: see text] with a Co—O bond length of 2.093(4)–2.113(5) Å, and [Ni(DMSO)6][SnCl6] (3), which crystallized in the trigonal R[Formula: see text] space group and has a Ni—O bond length of 2.062(2) Å. The Sn—Cl bond length in all three complexes ranged from 2.421(2) to 2.448(2) Å.Key words: DMSO complexes of Fe(II), Co(II) and Ni(II), SnCl62– salts, IR, Raman and Mössbauer spectroscopy, X-ray crystal structures.