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Towards Polysulfuric Acids: The Hydrogentrisulfate Anion [HS 3 O 10 ] − in A[HS 3 O 10 ] (A=Na, K, Rb)
Author(s) -
Schindler Lisa Verena,
Klüner Thorsten,
Wickleder Mathias S.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201602176
Subject(s) - orthorhombic crystal system , monoclinic crystal system , crystallography , chemistry , ion , sulfuric acid , rubidium , crystal structure , hydrogen bond , inorganic chemistry , molecule , potassium , organic chemistry
The reaction of Na 2 SO 4 and K 2 SO 4 with fuming sulfuric acid (65 % SO 3 ) yielded colorless extremely sensitive crystals of Na[HS 3 O 10 ] (monoclinic; P 2 1 / n (No. 14); Z =4; a =707.36(2), b =1378.56(4), c =848.10(3) pm; β =94.817(1)°; V =824.09(4) ⋅ 10 6 pm 3 ) and K[HS 3 O 10 ] (orthorhombic; Pccn (No. 56); Z =4; a =1057.16(3), b =807.81(2), c =897.57(2) pm; V =766.51(3) ⋅ 10 6 pm 3 ). The analogous rubidium compound Rb[HS 3 O 10 ] (orthorhombic; Pnma (No. 62); Z =4; a =891.43(3), b =1095.34(4), c =839.37(3) pm; V =819.58(5) ⋅ 10 6 pm 3 ) originates from the reaction of Rb 2 CO 3 and SO 3 . All of the different structures contain the hitherto unknown anion [HS 3 O 10 ] − and are stamped by strong hydrogen bonds linking the anions either to dimers or chains. Theoretical investigations by DFT methods give further insight in the structural characteristics of [HS 3 O 10 ] − . The preparation of the [HS 3 O 10 ] − anion can be seen as an important milestone on our way to the still elusive polysulfuric acids.