Abstract
With M(III)M(I)[B(SO(4))(2)](4) (M(III) = Bi(3+), Sb(3+), Lu(3+); M(I) = H(3)O(+), NO(2) (+), Li(+), Na(+), K(+), Rb(+), Cs(+)), we recently described the first modular system within borosulfate chemistry comprising a three-dimensional anion. Herein, we shed light on the respective series of antimony compounds SbX[B(SO(4))(2)](4) (X = Li(+), Na(+), K(+), Rb(+), Cs(+), Ag(+), Tl(+), NO(+), NH(4) (+)). While maintaining the same anionic topology, the compounds crystallize in the space groups I 4¯ (no. 82), P 4¯ (no. 81), and C2 (no. 5) and are strongly influenced by the lone pair of antimony as well as the size of the monovalent cations. In the course of this investigation SbX[B(4)O(2)(SO(4))(6)] (X = Li(+), Na(+)) were discovered. This borosulfate with a one-dimensional anion comprising B─O─B bridges crystallizes in the space group Pnma (no. 62) and features a new structure type. (121)Sb Mössbauer spectra revealed negative isomer shifts of almost -22 mm·s(-1) not observed before and hinting towards a very weak coordination behavior of the borosulfate anion. The spectra are confirmed by DFT calculations. Furthermore, single crystal X-ray diffraction, infrared spectroscopy, thermal analysis, and temperature programmed X-ray diffraction experiments were carried out.