Variability of a Non‐Centrosymmetric Tecto‐Borosulfate: Introduction of Various Molecular Cations into BiX[B(SO 4 ) 2 ] 4 (X = H 3 O + , NO 2 + , NH 4 + , NO + )

Although the number of borosulfates increased strongly over the past years, structures comprising a 3D anionic framework are still scarce. Herein, with BiX[B(SO 4 ) 2 ] 4 (X = NH 4 + , NO 2 + , NO + ) we present three new representatives. The bismuth borosulfates were synthesized under solvothermal condition and crystallize homeotypically to Bi(H 3 O)[B(SO 4 ) 2 ] 4 in the tetragonal space group I (Nr.82) ( a = 11.827(6) – 11.908(1) Å, c = 8.1160(2) – 8.1315(6) Å, Z = 2). Via all vertices connected BS 4 supertetrahedra reveal a zeolite type like structure like its found for the tectosilicate K 1.14 [Mg 0.57 Si 1.43 O 4 ] emphasizing their close relationship. Underlining the weak coordination behavior, for the first‐time nitrosonium and nitrosylium cations are introduced into borosulfate chemistry. SHG measurements confirm the absence of an inversion center and show a nonlinear optical response with intensities up to 1.4 times higher than KDP. Furthermore, the titled compounds were characterized thoroughly by both single‐crystal and powder X‐ray diffraction, infrared spectroscopy, density functional theory (DFT) calculations, and thermal analysis.