The Bismuth Hydrogen Sulfate [Bi₂(SO₄)₂(dmso)₈](HSO₄)₂

Abstract

The reaction of the basic bismuth nitrate [Bi6O4(OH)4(NO3)6]·H2O with either thiosalicylic acid or sulfuric acid gave the novel bismuth hydrogen sulfate [Bi2(SO4)2(dmso)8](HSO4)2 (1) (DMSO = dimethyl sulfoxide). The formation of sulfate ions is observed in the presence of either Bi3+ or [Bi6O4(OH)4]6+ indicating bismuth‐induced oxidation of thiosalicylic acid. Compound 1 was characterized by elemental analysis, infrared spectroscopy, thermal analysis (TGA), and temperature dependent in situ X‐ray powder diffraction. Crystals suitable for single crystal structure analysis were obtained from a DMSO/acetone solution. The title compound 1 crystallizes in the triclinic space group P$\bar{1}$ with the following lattice parameters: a = 9.5240(4) Å, b = 9.9535(4) Å, c = 12.6620(5) Å, α = 109.943(4)°, β = 93.952(3)°, γ = 102.868(3)°, V = 1086.17(8) Å3, and Z = 1. Analysis of the thermally induced decomposition revealed the formation of Bi2O(SO4)2 and Bi2O2(SO4) as intermediate products and Bi28O32(SO4)10 as final product.

Homo‐ and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates

“…Hence, in the IR spectrum of 4 , bands for the asymmetric ( =3010 cm −1 ) and symmetric stretching ( =2921 cm −1 ) and the asymmetric ( =1426 cm −1 ) and symmetric deformation vibrations ( =1412 cm −1 ) of the methyl groups of DMSO are observed . A very intense and broad band at =909 cm −1 results from S=O stretching and is characteristic for DMSO coordinated via the oxygen atom, as reported for other bismuth DMSO compounds . The broadening and slight downfield shift of the 1 H NMR signals of cluster 4 relative to the NMR spectra of 1 – 3 indicate a more dynamic behavior, decreasing covalency, and increasing degree of dissociation of the sulfonato ligands, which is reflected by elongated Bi−O bonds and an increased number of different coordination modes in the solid‐state structure.…”

“…[78] Av ery intense and broad band at ñ = 909 cm À1 results from S=Os tretching and is characteristic for DMSO coordinated via the oxygen atom, [78,79] as reportedf or other bismuth DMSO compounds. [39,55] Theb roadening and slight downfield shift of the 1 HNMR signals of cluster 4 relative to the NMR spectra of 1-3 indicateamore dynamic behavior,d ecreasing covalency, and increasing degree of dissociation of the sulfonato ligands, which is reflected by elongatedB i ÀOb onds anda ni ncreasedn umber of different coordination modes in the solid-states tructure. Three vinylsulfonato ligands( S3, S4, S9)e xclusively coordinate to the {Bi 6 } core by bridging the atoms Bi2, Bi5, and Bi6, which are located at the sterically accessible cluster site without lateralb ismuth atoms.…”

“…Hence, vinylsulfonic acid promotes partial degradation, whereas complete degradation is observed for stronger acids. For example, sulfuric acid (p K a =−3.19±0.15 (predicted), −2.5 (1,2‐dichloroethane), 8.7 (predicted, MeCN)) gives [Bi 2 (SO 4 ) 2 (dmso) 8 ](HSO 4 ) 2 in approaches A and B …”

“…(1,2-dichloroethane), [54] 8.7 (predicted, MeCN) [54] )g ives [Bi 2 (SO 4 ) 2 (dmso) 8 ](HSO 4 ) 2 in approaches A and B. [55] Structural characterization…”

Synthesis, Crystal Structures, Spectroscopic Characterization, and Thermal Analyses of the New Bismuth Sulfates NaBi(SO4)2·H2O and ABi(SO4)2 (A = K, Rb, Cs)

“…It's worth mentioning that KBiCl 2 (SO 4 ) [3] is the first bismuth chloride sulfate with second-order nonlinear optical effect. ( [13] Bi 2 O 2 (SO 4 ), [14] Bi 2 (SO 4 ) 3 , [15] Bi 26 O 27 (SO 4 ) 12 , [16] [Bi 2 (SO 4 ) 2 (dmso) 8 ](HSO 4 ) 2 , [17] [Bi 14 O 16 ](SO 4 ) 5 , [18] [Bi 2 CoO 3 (SO 4 )], [19] [Bi 12.67 O 14 ](SO 4 ) 5 , [20] alkali metal cations are located between the layers or in the tunnels of the structures, respectively. The differences in the crystal structures of the title compounds can mainly be attributed to the different sizes of the alkali metal cations and their different coordination environments.…”