The Borosulfates K4[BS4O15(OH)], Ba[B2S3O13], and Gd2[B2S6O24]

K4 [BS4 O15 (OH)], Ba[B2 S3 O13 ], and Gd2 [B2 S6 O24 ] were obtained by a new synthetic approach. The strategy involves initially synthesizing the complex acid H[B(HSO4 )4 ] which is subsequently reacted in an open system with anhydrous chlorides of K, Ba, and Gd to the respective borosulfates and a volatile molecule (HCl). Furthermore, protonated borosulfates should be accessible by appropriate stoichiometry of the starting materials, particularly in closed systems, which inhibit deprotonation of H[B(HSO4 )4 ] via condensation and dehydration. This approach led to the successful synthesis of the first divalent and trivalent metal borosulfates (Ba[B2 S3 O13 ] with band-silicate topology and Gd2 [B2 S6 O24 ] with cyclosilicate topology) and the first hydrogen borosulfate K4 [BS4 O15 (OH)].