Borosulfate

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The borosulfates are heteropoly anion compounds which have sulfate groups attached to boron atoms. Other possible terms are sulfatoborates or boron-sulfur oxides. The ratio of sulfate to borate reflects the degree of condensation. With [B(SO4)4]5- there is no condensation, each ion stands alone. In [B(SO4)3]3- the anions are linked into a chain, a chain of loops, or as [B2(SO4)6]6− in a cycle. Finally in [B(SO4)2]− the sulfate and borate tetrahedra are all linked into a two or three-dimensional network. These arrangements of oxygen around boron and sulfur can have forms resembling silicates. The first borosulfate to be discovered was K5[B(SO4)4] in 2012 by the research group of Henning Höppe, [1] [2] although the compound class as such had been postulated already in 1962 by G. Schott and H. U. Kibbel. [3] Over 80 unique compounds are known as of 2024.

Contents

They are distinct from the borate sulfates which have separate, uncondensed sulfate and borate ions.

Related compounds include boroselenates, borotellurates, [4] and also boroantimonates, borogallates, borogermanates, borophosphates, boroselenites and borosilicates. [5]

Formation

Borosulfates are formed by heating boric oxide, oleum, or sulfuric acid, with metal carbonates. The degree of condensation is varied with the ratio of oleum to sulfuric acid. Pure oleum is more likely to yield compounds with disulfate groups.

Reactions

When heated to around 500 °C the borosulfates decompose by emitting SO3 vapour and form a metal sulfate and boric oxide. [6]

List

chemmwcrystal systemspace groupunit cell Åvolumedensitycommentreferences
boron sulfateB2S2O9229.74 monoclinic C2a=7.7600 b=4.1664 c=8.6134 β=94.785 Z=2277.512.749no cations; 3D mesh [7]
H[B(HSO4)4]monoclinicP21/ca=15.6974, b=11.436, c=8.5557; β=90.334°; Z=8superacid [8] [9]
H3O[B(SO4)2]P4/ncca=9.1377, c=7.3423; Z=4 [9]
H[B(SO4)(S2O7)]monoclinicP21/ca=15.697 b=11.4362 c=8.5557 β=90.334 [4]
Li[B(SO4)2]Pca = 7.635, b = 9.342, c = 8.432, and β = 92.55°3D network, like tectosilicate [8] [10]
Li[B(S2O7)2] orthorhombic P212121a = 10.862, b = 10.877, c = 17.769 [8] [10]
Li5[B(SO4)4]orthorhombicP21/ca=8.0191 b=10.2111 c=15.0401 [4]
Be[B2(SO4)4]monoclinicC2/ca= 23.856, b= 7.3507, c= 12.3235, β= 98.724(2)°, Z=82136.12.58colourless [11]
NH4[B(SO4)2]P4/ncca=9.1980 c=7.2458decompose 320 °C, proton conductor [4] [12]
NH4[B(S2O7)2]monoclinicCca=11.4403 b=14.9439 c=13.8693 β=93.662 [8] [4]
(NH4)2B4SO10271.38monoclinicC2a=11.3685 b=6.5541 c=12.8328 β=106.247 4918.01.964SHG 1.1 × KDP; min PM wavelength 252 nm; decompose 300 °C [13]
[NH4]3[B(SO4)3]343.12orthorhombicIbcaa=7.2858 b=14.7048 c=22.7052 Z=82433.21.928decompose 320 °C chains [14] [2]
Na[B(SO4)2]monoclinicP2/ca=5.434 b=7.570 c=7.766 β=99.74 [4]
Na[B(S2O7)2]monoclinicP21/ca=10.949, b=8.49, c=12.701; β=110.227°; Z=4 [8] [9]
Na2B6SO13orthorhombicPbcaa=11.6569 b=9.4094 c=17.4833 Z=81917.62.431birefringence Δn = 0.07 @ 589.3 nm [15]
Na5[B(SO4)4]-IorthorhombicPca21a = 10.730, b = 13.891, c = 18.197 [10]
Na5[B(SO4)4]-IIorthorhombicP212121a = 8.624, b = 9.275, c = 16.671 [10]
α-Mg4[B2O(SO4)6]711.22 trigonal P3a=8.0165 c=7.4858 Z=1416.622.835colourless [6]
β-Mg4[B2O(SO4)6]711.22 hexagonal P3a = 13.9196, c = 7.4854, Z = 312532.821colourless [6]
Mg[B2(SO4)4]430.17monoclinicC2/ca = 17.443, b = 5.3145, c = 14.2906 β = 126.323° Z = 41067.32.677 phyllosilicate structure colourless decompose 550 °C [6]
β-Mg[B2(SO4)4]monoclinicP21/na=7.9100 b=8.0815 c=9.0376 β=111.37° Z=2269.012.667colourless decompose 550 °C [16]
Mg3((H2O)B(SO4)3)2706.94triclinicP1a=7.9609 b=7.9671 c=9.2343 α=64.959° β=89.228° γ=60.054°444.962.638200K [15]
Mg3((H2O)B(SO4)3)2706.94R3a=7.9620 c=24.4231 Z=31340.842.627room temperature [15]
K[B(SO4)2]P4/ncca=8.9739 c=7.4114 [4]
K[B(S2O7)2]monoclinicCca=11.3368, b=14.66, c=13.6650; β=94.235°; Z=8 [8] [9]
K2B4SO10313.50monoclinicC2a=11.2631 b=6.4339 c=12.649 β=105.707° Z=4882.42.360colourless [17]
pentapotassium borosulfateK5[B(SO4)4]P41a=9.9023 c=16.18711687.22.471first discovered [8] [1]
K3[B(SO4)3]orthorhombicIbcaa = 7.074, b = 14.266, c = 22.58 [8] [10]
K4[BS4O15(OH)]monoclinicI2/aa=14.524 b=7.3916 c=15.7857 β=115.50 [4]
CaB2S4O16monoclinicP21/ca=5.5188 b=15.1288 c=13.2660 β=92.88sheet [4]
Mn[B2(SO4)4]monoclinicP21/na = 8.0435, b = 7.9174, c = 9.3082, β = 110.94° Z=2553.63colourless [18]
α-Mn4[B2O(SO4)6]833.74trigonalP3a=8.1086 c=7.7509 Z=1441.33.137colourless [6]
β-Mn4[B2O(SO4)6]833.74trigonalP3a=13.9196 c=7.4854
α-Co[B2(SO4)4]monoclinicC2/ca=17.4254 b=5.3397 c=14.3214 β=126.03° Z=4269.402.860pink [16]
β-Co[B2(SO4)4]monoclinicP21/na=7.8892 b=8.1042 c= 9.0409 β=111.29° Z=2269.292.803pink [16]
α-Co4[B2O(SO4)6]849.70trigonalP3a=7.991 c=7.669 Z=1418.03.376pink [6]
α-Ni4[B2O(SO4)6]848.82trigonalP3a=7.9359 c=7.4398 Z=1405.773.474yellow [6]
Cu[B(SO4)2(HSO4)] triclinic P1a=5.3096 b=7.0752 c=11.1977 α=81.154 β=80.302 γ=80.897cyclic [4]
Cu[B2(SO4)4]triclinicP1a=5.2470 b=7.1371 c=7.9222 α=73.814 β=70.692 γ=86.642chain [4]
Zn[B2(SO4)4]monoclinicP21/na = 8.0435, b = 7.9174, c = 9.3082, β = 111.26° Z=2534.36colourless [18]
α-Zn4[B2O(SO4)6]875.46trigonalP3a=7.9971 c=7.4895 Z=1414.813.505colourless [6]
Rb2B4SO10406.24monoclinicC2a=11.3127 b=6.5152 c=12.971 β=105.411° Z=4921.62.928colourless [17]
Rb3[B(SO4)3]orthorhombicIbcaa = 7.2759, b = 14.794, c = 22.637 [10]
Rb4[B2O(SO4)4]orthorhombicPnmaa=8.0415 b=10.647 c=20.425 [4]
Rb5[B(SO4)4]tetragonalP43212a=10.148 c=16.689 Z=4band gap 3.99 eV [4] [19]
Rb3HB4S2O14P63/ma = 6.502, c = 19.02 Z=2 [20]
LiRb4[B(SO4)4]743.8monoclinicP21a=7.5551, c=14.560, c=7.5517 β=90.2372 Z=2transparent [21]
LiRb4[B(SO4)4]743.8tetragonalI4a=7.6128, c=14.631, Z=2at 500K [21]
Sr[B2(SO4)4]493.48orthorhombicPnmaa=12.574 b=12.421 c=7.319 Z=41143.12.867decompose 400 °C [8] [2]
Sr[B2(SO4)3(S2O7)]573.54monoclinicP21/na = 7.470, b = 15.334, c = 12.220, β = 93.29° Z=41397.52.726 [8]
Sr[B2O(SO4)3]orthorhombicPnmaa=1657.3 b=12.037 c=4.39484 [8] [4]
Sr[B3O(SO4)4(SO4H)]617.36monoclinicP21/ca = 11.3309, b= 7.1482, c = 19.355, β = 106.878°, Z = 41500.12.73colourless; Sr in 9 coordination by sulfate oxygens [22]
Y2[B2(SO4)6]monoclinicC2/ca=13.5172 b=11.3941 c=10.8994 β=93.447cyclic [14] [4]
Ag[B(SO4)2]P4/ncca=8.6679 c=7.2897 [4]
Ag[B(S2O7)2]monoclinicP21/ca = 9.507, b = 9.601, c = 11.730, β = 98.35° Z=41059.32.953colourless [23]
Cd[B2(SO4)4] [24]
Cd[B2O(SO4)3]438.20orthorhombicPnmaa=8.9692 b=11.520 c=8.7275 Z=4901.83.23colourless [24]
Cd4[B2O(SO4)6]trigonalP3a=8.2222 c=7.9788 Z=1467.143.78colourless [24]
(I4)[B(S2O7)2]2triclinicP1a = 11.3714 b = 11.5509 c = 12.7811 α = 68.638° β = 68.275° γ = 64.626° Z=21366.162.999orange-brown [25]
Cs2B4SO10501.12monoclinicC2a=11.4012 b=6.5997 c=13.5702 β=103.934° Z=4919.043.359colourless [17]
Cs2[B2O(SO4)3]monoclinicP2/ca=14.765 b=6.710 c=12.528 β=104.50 [20]
Cs3HB4S2O14P63/ma = 6.5648, c = 19.5669 Z=2 [20]
Cs[B(SO4)(S2O7)]monoclinicP21/ca=10.4525, b=11.319, c=8.2760; β=103.206; Z=4 [8] [9]
Cs3Li2[B(SO4)4]monoclinicP21/na=13.7698 c=8.2376 c=13.9066 β=91.778 [14] [4]
Cs3Na2[B(SO4)4]monoclinicP21/ca=13.6406 b=7.9475 c=13.9573 β=990.781 [14] [4]
CsK4[B(SO4)4]P43212a=9.9433 c=16.881 [14] [4]
Ba[B2(SO4)4]orthorhombicPnnaa = 12.791, b = 12.800, c = 7.317 Z = 4 [8] [26]
Ba[B2O(SO4)3]orthorhombicPnmaa=17.1848 b=12.3805 c=4.4226 [8]
Ba[B(S2O7)2]2monoclinicI2/aa = 11.6077, b = 8.9144, c = 21.303, β = 104.034° Z = 4chains [8] [26]
La2[B2(SO4)6]monoclinicC2/ca=1379.2 b=1158.9 c=1139.5 β=93.611cyclic [14] [4]
Ce2[B2(SO4)6]monoclinicC2/c13.740 b=11.5371 c=11.3057 β=93.661cyclic [14] [4]
Pr2[B2(SO4)6]monoclinicC2/ca=13.711 b=11.5305 c=11.2643 β=93.668cyclic [14] [4]
Nd2[B2(SO4)6]monoclinicC2/ca=13.6775 b=11.51.34 11.2046 β=93.5909cyclic [14] [4]
Sm2[B2(SO4)6]monoclinicC2/ca=13.633 b=11.492 c=11.112 β=93.567cyclic [14] [4]
Eu2[B2(SO4)6]monoclinicC2/ca=13.602 b=11.470 c=11.050 β=93.465cyclic [14] [4]
Gd2[B2(SO4)6]monoclinicC2/ca=13.5697 b=11.4426 c=11.0271 β=cyclic [14] [4]
Tb2[B2(SO4)6]monoclinicC2/ca=13.5601 b=11.42.48 c=10.9881 β=93.534cyclic [14] [4]
Dy2[B2(SO4)6]monoclinicC2/ca=13.568 b=11.425 c=10.9703 β=93.540cyclic [14] [4]
Ho2[B2(SO4)6]monoclinicC2/ca=13.505 b=11.409 c=10.921 β=93.453cyclic [14] [4]
Er2[B2(SO4)6]monoclinicC2/ca=13.551 b=11.411 c=10.882 β=93.41cyclic [14] [4]
Tm2[B2(SO4)6]monoclinicC2/ca=13.4981 b=11.3617 10.8327 β=93.4500cyclic [14] [4]
Yb2[B2(SO4)6]monoclinicC2/ca=13.495 b=11.3452 c=10.7961 β=93.390cyclic [14] [4]
Lu2[B2(SO4)6]monoclinicC2/ca=13.469 b=11.364 c=10.799 β=93.369cyclic [14] [4]
Pb[B2(SO4)4]613.05orthorhombicPnnaa=12.516 b=12.521 c=7.302 Z=4114.433.558loop chain [4] [27]
Pb[B2O(SO4)3]orthorhombicP21/ma=4.4000 b=12.1019 c=8.6043 [4]
Bi2[B2(SO4)6]659.08orthorhombicC2/ca = 13.568, b = 11.490, c = 11.106 Z=41728.83.894 [14]
(H3O)Bi[B(SO4)2]41039.72I4a=11.857, c=8.149 Z=21156.842.99colourless; non-linear optical [14]
(UO2)[B(SO4)2(SO3OH)]569.52triclinicP1a=5.448 b=7.021 c=13.522 α =92.248° β =95.347° γ =101.987° Z=23.762green [28]
(UO2)2[B2O(SO4)3(SO3OH)2]1058.23monoclinicP21/na=10.872 b=11.383 c=14.812 β=92.481 Z=43.838yellow [28]

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References

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  3. ↑ Schott, G.; Kibbel, H. U. "Über Sulfatoborate". Zeitschrift für anorganische und allgemeine Chemie. 314 (1–2): 104–112. doi:10.1002/zaac.19623140113. ISSN   0044-2313.
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  5. ↑ Kong, Fang; Ma, Yunxiang; Mao, Jianggao (January 2018). "Lanthanide Inorganic Solids Based on Main Group Borates and Oxyanions of Lone Pair Cations: Lanthanide Inorganic Solids Based on Main Group Borates and Oxyanions of Lone Pair Cations". Chinese Journal of Chemistry. 36 (1): 63–72. doi:10.1002/cjoc.201700597.
  6. 1 2 3 4 5 6 7 8 Netzsch, Philip; Gross, Peter; Takahashi, Hirotaka; Höppe, Henning A. (2018-07-16). "Synthesis and Characterization of the First Borosulfates of Magnesium, Manganese, Cobalt, Nickel, and Zinc". Inorganic Chemistry. 57 (14): 8530–8539. doi:10.1021/acs.inorgchem.8b01234. ISSN   0020-1669. PMID   29957944.
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  11. ↑ Sutorius, Stefan; Hanrath, Michael; Bruns, Jörn (2022-02-09). "Be[B2(SO4)4] – A Borosulfate exhibiting Ino- and Phyllosilicate Analogue Topology". European Journal of Inorganic Chemistry. 2022 (11): ejic.202200009. doi: 10.1002/ejic.202200009 . ISSN   1434-1948. S2CID   246719711.
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  13. ↑ Li, Zijian; Jin, Wenqi; Zhang, Fangfang; Chen, Zilong; Yang, Zhihua; Pan, Shilie (2021-10-09). "Achieving Short-Wavelength Phase-Matching Second Harmonic Generation in Boron-Rich Borosulfate with Planar [BO3] Units". Angewandte Chemie International Edition. 61 (4): anie.202112844. doi:10.1002/anie.202112844. ISSN   1433-7851. PMID   34626043. S2CID   238528455.
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  19. ↑ Dong, Lingyun; Pan, Shilie; Wang, Ying; Yu, Hongwei; Lin, Xiaoxia; Han, Shujuan (March 2015). "Synthesis and structural characterization of a new rubidium borosulfate, Rb5BS4O16". Materials Research Bulletin. 63: 93–98. doi:10.1016/j.materresbull.2014.11.047.
  20. 1 2 3 Daub, Michael; Hillebrecht, Harald (September 2015). "Borosulfates Cs 2 B 2 S 3 O 13 , Rb 4 B 2 S 4 O 17 , and A 3 HB 4 S 2 O 14 ( A = Rb, Cs) – Crystalline Approximants for Vitreous B 2 O 3 ?". European Journal of Inorganic Chemistry. 2015 (25): 4176–4181. doi:10.1002/ejic.201500603. ISSN   1434-1948.
  21. 1 2 Li, Yanqiang; Zhou, Zhengyang; Zhao, Sangen; Liang, Fei; Ding, Qingran; Sun, Junliang; Lin, Zheshuai; Hong, Maochun; Luo, Junhua (2021-03-08). "A Deep-UV Nonlinear Optical Borosulfate with Incommensurate Modulations". Angewandte Chemie International Edition. 60 (20): 11457–11463. doi:10.1002/anie.202102107. ISSN   1433-7851. PMID   33686736. S2CID   232160602.
  22. ↑ Pasqualini, Leonard; Huppertz, Hubert; Je, Minyeong; Choi, Heechae; Bruns, Jörn (2021-06-13). "Triple Vertex Linkage of (BO4)-Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum Chemical Investigation of Sr[B3O(SO4)4(SO4H)]". Angewandte Chemie International Edition. 60 (36): 19740–19743. doi: 10.1002/anie.202106337 . ISSN   1433-7851. PMC   8456809 . PMID   34121302.
  23. ↑ Netzsch, Philip; Höppe, Henning A. (2020-12-29). "Ag[B(S2O7)2]: The First Transition Metal Borosulfate Featuring Disulfate Groups". European Journal of Inorganic Chemistry. 2021 (11): 1065–1070. doi: 10.1002/ejic.202001095 . ISSN   1434-1948.
  24. 1 2 3 Hämmer, Matthias; Höppe, Henning A. (2022-09-02). "The Unconventional Cadmium Borosulfates Cd[B2O(SO4)3] and Cd4[B2O(SO4)6]". Zeitschrift für anorganische und allgemeine Chemie. 648 (21): zaac.202200197. doi: 10.1002/zaac.202200197 . ISSN   0044-2313. S2CID   252059729.
  25. ↑ van Gerven, David; Sutorius, Stefan; Bruns, Jörn; Wickleder, Mathias S. (2022-07-20). "Stabilizing the Homopolycation (I 4 ) 2+ with a Hexasulfate in (I 4 )[S 6 O 19 ] and a Borosulfate in (I 4 )[B(S 2 O 7 ) 2 ] 2". ChemistryOpen. 11 (11): e202200122. doi:10.1002/open.202200122. ISSN   2191-1363. PMC   9630045 . PMID   35856862. S2CID   250941699.
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  27. ↑ Schönegger, Sandra; Bruns, Jörn; Gartner, Benjamin; Wurst, Klaus; Huppertz, Hubert (2018-12-31). "Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B 2 (SO 4 ) 4 ]: Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B 2 (SO 4 ) 4 ]". Zeitschrift für anorganische und allgemeine Chemie. 644 (24): 1702–1706. doi: 10.1002/zaac.201800130 .
  28. 1 2 Sweet, Teagan F. M.; Felton, Daniel E.; Szymanowski, Jennifer E. S.; Burns, Peter C. (2022-09-01). "Targeting Diverse Bridging Motifs within Actinide Borosulfates and Establishing an Unconventional Structural Hierarchy". Inorganic Chemistry. 61 (40): 15953–15960. doi:10.1021/acs.inorgchem.2c02144. ISSN   0020-1669. PMID   36047685. S2CID   251977898.
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