The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate‐Analogous Anion

Abstract

The first bismuth borosulfate (H 3 O)Bi[B(SO 4 ) 2 ] 4 is only the second featuring a three‐dimensional anion, the first tectosilicate‐analogous borosulfate synthesised solvothermally without a precursor (from Bi(NO 3 ) 3 ⋅5 H 2 O and B(OH) 3 in oleum); moreover, it is the first comprising two differently charged cations and crystallises in a new structure type in space group I (no. 82) (a=11.857(1), c=8.149(1) Å, 1947 refl., 111 param., wR2=0.037), confirmed by a second harmonic generation (SHG) measurement. The B(SO 4 ) 4 supertetrahedra are connected via all four sulfate tetrahedra resulting in a three‐dimensional anion with both H 3 O + and Bi 3+ cations in channels. Additionally, the crystal structure of a further bismuth borosulfate, Bi 2 [B 2 (SO 4 ) 6 ], is elucidated crystallising isotypically to the rare‐earth borosulfates R 2 [B 2 (SO 4 ) 6 ] in space group C2/c (No. 15) (a=13.568(2), b=11.490(2), c=11.106(2) Å, 3127 refl., 155 param., wR2=0.035). Moreover, the optical and thermal properties of both compounds are discussed.

Polymorphism and optical, magnetic and thermal properties of the either phyllo- or inosilicate-analogous borosulfate Cu[B2(SO4)4]

“…The latter was recently reported for the lone pair effect of Bi 3+ cations in Bi 2 [B 2 (SO 4 ) 6 ]. 6 The electrostatic reasonability of the crystal structure of α-Cu[B 2 (SO 4 ) 4 ] was confirmed by calculations based on the MAPLE concept. 31–34 The MAPLE values of α-Cu[B 2 (SO 4 ) 4 ] were calculated and compared to the sum of the MAPLE values of CuSO 4 , B 2 S 2 O 9 and SO 3 , respectively (Table S16†).…”

“…The absence of an inversion centre within tetrahedra often leads to interesting optical properties as they foster non-centrosymmetric coordination environments around emitting cations and thus promote high luminescence probabilities or even nonlinear optical properties if the whole structure lacks inversion symmetry. 1,3–7 With the first crystalline borosulfate K 5 [B(SO 4 ) 4 ] discovered as recent as 2012, 8 there are over seventy compounds characterised to date. 7,9–15 Borosulfates may be classified as silicate-analogous 16 in two ways: on the one hand, their anions consist most commonly 15 of corner sharing borate and sulfate tetrahedra, solely.…”

“…For that, Friedrich Liebau's classification of silicates is adapted. 16 There are borosulfates with 0D anions like the cyclosilicate-analogous M 2 [B 2 (SO 4 ) 6 ] (M = Y, La–Nd, Sm–Lu, Bi) 5,6,17 or the nesosilicate-analogous K 5 [B(SO 4 ) 4 ], 8 1D anions like the inosilicate-analogous (NH 4 ) 3 [B(SO 4 ) 3 ], 10 2D anions like the phyllosilicate-analogous α- and β-M[B 2 (SO 4 ) 4 ] (M = Mg, Co) 11,14,18 and 3D anions like the tectosilicate-analogous Bi(H 3 O)[B(SO 4 ) 2 ] 4 . 6 In contrast to these so-called conventional borosulfates, there are unconventional borosulfates comprising S–O–S or B–O–B bridges like Sr[B 2 (SO 4 ) 3 (S 2 O 7 )] 9 and Mg 4 [B 2 O(SO 4 ) 6 ] 18 violating Pauling's fourth 19 and Loewenstein's rules, 20 respectively.…”

Die ersten zwei Bismutborosulfate – eines davon enthält Oxonium und ein tektosilicatanaloges Anion

“…Refinement details are summarised in Table S1. [38] Figures 1 a and 1 b display the unit cell of the title compound. The anion consists of TX 4 supertetrahedra (T = B, X = SO 4 ) sharing all four corners with neighbouring ones yielding a 3D network.…”

Ag[B(S2O7)2]: The First Transition Metal Borosulfate Featuring Disulfate Groups

“…Starting from the first borosulfate K 5 [B(SO 4 ) 4 ] eight years ago [2] ongoing research led to enormous progress in borosulfate chemistry. Besides the structural evolution, especially optical properties were investigated showing a weak coordination behavior of the borosulfate anions [3–5] or even second harmonic generation responses [6] . A striking prospect for borosulfate chemistry, however, could be as electrolytes for solid acid fuel cells, since a high proton conductivity for the ammonium borosulfates NH 4 [B(SO 4 ) 2 ] was reported, recently [7] .…”