Crystal structure and optical absorption spectra of LiCo(SO4)OH and its remarkable relationship to the Zn-Mn-silicate hodgkinsonite

Abstract

Crystals of the compound LiCo(SO4)OH were synthesised at low-hydrothermal conditions, and the crystal structure was determined and refined from single crystal X-ray diffraction data. LiCo(SO4)OH crystallises monoclinic, space group P21/c, Z = 4, a = 9.586(2), b = 5.425(1), c = 7.317(1) Å, β = 109.65(1)°, V = 358.3 Å3, wR2 = 0.0485 (2215 unique reflections, 78 variables). The structure is built from chains of edge-sharing, quite strongly bond-length and -angle distorted Co(OH)3O3 octahedra (< Co–O > = 2.126 Å), which are further linked by common corners, hydrogen bonds, and by properly shaped SO4 tetrahedra (< S–O > = 1.476 Å) to sheets parallel (100). These sheets are connected to a three-dimensional framework by sharing corners with distorted LiO4 polyhedra (< Li–O > = 1.956 Å). Apart from the isotypic sulfates of Mn2+ and Fe2+, only the molybdate LiCd(MoO4)OH crystallises isostructural with LiCo(SO4)OH. However, a very close structural relationship exists with the rare mineral hodgkinsonite, Zn2Mn(SiO4)(OH)2, yielding crystal chemically very uncommon topological equivalents of Zn2+ ≡ S6+ and Si4+ ≡ Li+, aside from the expectable substitution Mn2+ ≡ Co2+. Polarised optical absorption spectra of LiCo(SO4)OH reveal that the dominating spin-allowed 4T1(P) band system of Co2+ (d7 configuration) is strongly split up and covers a prominent part (~ 15,500–24,500 cm−1) of the visible spectral range, in accordance with the significant distortion of the Co(OH)3O3 polyhedron. The spectra are interpreted in terms of the Superposition Model of crystal fields, yielding a new set of intrinsic and interelectronic repulsion parameters for Co2+.