The Borosulfate Story Goes on-From Alkali and Oxonium Salts to Polyacids

Abstract

The structural principles of borosulfates derived from the B/S ratio are confirmed and extended to new representatives of this class showing novel motifs. According to the composition, Na[B(S2O7)2] (P2(1)/c; a=10.949(6), b=8.491(14), c=12.701(8) Å; β=110.227(1)°; Z=4) and K[B(S2O7)2] (Cc; a=11.3368(6), b=14.662(14), c=13.6650(8) Å; β=94.235(1)°; Z=8) contain isolated [B(S2O7)2](-) ions, in which the central BO4 tetrahedron is coordinated by two disulfate units. The alkali cations have coordination numbers of 7 (Na) and 8 (K), respectively. The structure of Cs[B(S2O7)(SO4)] (P2(1)/c; a=10.4525(6), b=11.3191(14), c=8.2760(8) Å; β=103.206(1); Z=4) combines, for the first time, sulfate and disulfate units into a chain structure. Cs has a coordination number of 12. The same structural units were found in H[B(S2O7)(SO4)] (P2(1)/c; a=15.6974(6), b=11.4362(14), c=8.5557(8) Å; β=90.334(3)°; Z=8). This compound represents the first example of a polyacid. The hydrogen atoms were located and connect the chains to form layers through hydrogen-bonding bridges. H3O[B(SO4)2] (P4/ncc; a=9.1377(6), c=7.3423(8) Å; Z=4) is the first oxonium compound of this type to be found. The BO4 tetrahedra are linked by SO4 tetrahedra to form linear chains similar to those in SiS2. The chains form a tetragonal rod packing structure with H3O(+) between the rods. The structures of borosulfates can be classified following the concept described by Liebau for silicates, which was extended to borophosphates by Kniep et al. In contrast to these structures, borosulfates do not comprise B-O-B bonds but instead contain S-O-S connections. All compounds were obtained as colourless, moisture-sensitive single crystals by reaction of B2O3 and the appropriate alkali salt in oleum.