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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.

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

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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

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

List

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chem mw crystal system space group unit cell Å volume density comment references
boron sulfate B2S2O9 229.74 monoclinic C2 a=7.7600 b=4.1664 c=8.6134 β=94.785 Z=2 277.51 2.749 no cations; 3D mesh [7]
H[B(HSO4)4] monoclinic P21/c a=15.6974, b=11.436, c=8.5557; β=90.334°; Z=8 superacid [8][9]
H3O[B(SO4)2] P4/ncc a=9.1377, c=7.3423; Z=4 [9]
H[B(SO4)(S2O7)] monoclinic P21/c a=15.697 b=11.4362 c=8.5557 β=90.334 [4]
Li[B(SO4)2] Pc a = 7.635, b = 9.342, c = 8.432, and β = 92.55° 3D network, like tectosilicate [8][10]
Li[B(S2O7)2] orthorhombic P212121 a = 10.862, b = 10.877, c = 17.769 [8][10]
Li5[B(SO4)4] orthorhombic P21/c a=8.0191 b=10.2111 c=15.0401 [4]
Be[B2(SO4)4] monoclinic C2/c a= 23.856, b= 7.3507, c= 12.3235, β= 98.724(2)°, Z=8 2136.1 2.58 colourless [11]
NH4[B(SO4)2] P4/ncc a=9.1980 c=7.2458 decompose 320 °C, proton conductor [4][12]
NH4[B(S2O7)2] monoclinic Cc a=11.4403 b=14.9439 c=13.8693 β=93.662 [8][4]
(NH4)2B4SO10 271.38 monoclinic C2 a=11.3685 b=6.5541 c=12.8328 β=106.247 4 918.0 1.964 SHG 1.1 × KDP; min PM wavelength 252 nm; decompose 300 °C [13]
[NH4]3[B(SO4)3] 343.12 orthorhombic Ibca a=7.2858 b=14.7048 c=22.7052 Z=8 2433.2 1.928 decompose 320 °C chains [14][2]
Na[B(SO4)2] monoclinic P2/c a=5.434 b=7.570 c=7.766 β=99.74 [4]
Na[B(S2O7)2] monoclinic P21/c a=10.949, b=8.49, c=12.701; β=110.227°; Z=4 [8][9]
Na2B6SO13 orthorhombic Pbca a=11.6569 b=9.4094 c=17.4833 Z=8 1917.6 2.431 birefringence Δn = 0.07 @ 589.3 nm [15]
Na5[B(SO4)4]-I orthorhombic Pca21 a = 10.730, b = 13.891, c = 18.197 [10]
Na5[B(SO4)4]-II orthorhombic P212121 a = 8.624, b = 9.275, c = 16.671 [10]
α-Mg4[B2O(SO4)6] 711.22 trigonal P3 a=8.0165 c=7.4858 Z=1 416.62 2.835 colourless [6]
β-Mg4[B2O(SO4)6] 711.22 hexagonal P3 a = 13.9196, c = 7.4854, Z = 3 1253 2.821 colourless [6]
Mg[B2(SO4)4] 430.17 monoclinic C2/c a = 17.443, b = 5.3145, c = 14.2906 β = 126.323° Z = 4 1067.3 2.677 phyllosilicate structure colourless decompose 550 °C [6]
β-Mg[B2(SO4)4] monoclinic P21/n a=7.9100 b=8.0815 c=9.0376 β=111.37° Z=2 269.01 2.667 colourless decompose 550 °C [16]
Mg3((H2O)B(SO4)3)2 706.94 triclinic P1 a=7.9609 b=7.9671 c=9.2343 α=64.959° β=89.228° γ=60.054° 444.96 2.638 200K [15]
Mg3((H2O)B(SO4)3)2 706.94 R3 a=7.9620 c=24.4231 Z=3 1340.84 2.627 room temperature [15]
K[B(SO4)2] P4/ncc a=8.9739 c=7.4114 [4]
K[B(S2O7)2] monoclinic Cc a=11.3368, b=14.66, c=13.6650; β=94.235°; Z=8 [8][9]
K2B4SO10 313.50 monoclinic C2 a=11.2631 b=6.4339 c=12.649 β=105.707° Z=4 882.4 2.360 colourless [17]
pentapotassium borosulfate K5[B(SO4)4] P41 a=9.9023 c=16.1871 1687.2 2.471 first discovered [8][1]
K3[B(SO4)3] orthorhombic Ibca a = 7.074, b = 14.266, c = 22.58 [8][10]
K4[BS4O15(OH)] monoclinic I2/a a=14.524 b=7.3916 c=15.7857 β=115.50 [4]
CaB2S4O16 monoclinic P21/c a=5.5188 b=15.1288 c=13.2660 β=92.88 sheet [4]
Mn[B2(SO4)4] monoclinic P21/n a = 8.0435, b = 7.9174, c = 9.3082, β = 110.94° Z=2 553.63 colourless [18]
α-Mn4[B2O(SO4)6] 833.74 trigonal P3 a=8.1086 c=7.7509 Z=1 441.3 3.137 colourless [6]
β-Mn4[B2O(SO4)6] 833.74 trigonal P3 a=13.9196 c=7.4854
α-Co[B2(SO4)4] monoclinic C2/c a=17.4254 b=5.3397 c=14.3214 β=126.03° Z=4 269.40 2.860 pink [16]
β-Co[B2(SO4)4] monoclinic P21/n a=7.8892 b=8.1042 c= 9.0409 β=111.29° Z=2 269.29 2.803 pink [16]
α-Co4[B2O(SO4)6] 849.70 trigonal P3 a=7.991 c=7.669 Z=1 418.0 3.376 pink [6]
α-Ni4[B2O(SO4)6] 848.82 trigonal P3 a=7.9359 c=7.4398 Z=1 405.77 3.474 yellow [6]
Cu[B(SO4)2(HSO4)] triclinic P1 a=5.3096 b=7.0752 c=11.1977 α=81.154 β=80.302 γ=80.897 cyclic [4]
Cu[B2(SO4)4] triclinic P1 a=5.2470 b=7.1371 c=7.9222 α=73.814 β=70.692 γ=86.642 chain [4]
Zn[B2(SO4)4] monoclinic P21/n a = 8.0435, b = 7.9174, c = 9.3082, β = 111.26° Z=2 534.36 colourless [18]
α-Zn4[B2O(SO4)6] 875.46 trigonal P3 a=7.9971 c=7.4895 Z=1 414.81 3.505 colourless [6]
Rb2B4SO10 406.24 monoclinic C2 a=11.3127 b=6.5152 c=12.971 β=105.411° Z=4 921.6 2.928 colourless [17]
Rb3[B(SO4)3] orthorhombic Ibca a = 7.2759, b = 14.794, c = 22.637 [10]
Rb4[B2O(SO4)4] orthorhombic Pnma a=8.0415 b=10.647 c=20.425 [4]
Rb5[B(SO4)4] tetragonal P43212 a=10.148 c=16.689 Z=4 band gap 3.99 eV [4][19]
Rb3HB4S2O14 P63/m a = 6.502, c = 19.02 Z=2 [20]
LiRb4[B(SO4)4] 743.8 monoclinic P21 a=7.5551, c=14.560, c=7.5517 β=90.2372 Z=2 transparent [21]
LiRb4[B(SO4)4] 743.8 tetragonal I4 a=7.6128, c=14.631, Z=2 at 500K [21]
Sr[B2(SO4)4] 493.48 orthorhombic Pnma a=12.574 b=12.421 c=7.319 Z=4 1143.1 2.867 decompose 400 °C [8][2]
Sr[B2(SO4)3(S2O7)] 573.54 monoclinic P21/n a = 7.470, b = 15.334, c = 12.220, β = 93.29° Z=4 1397.5 2.726 [8]
Sr[B2O(SO4)3] orthorhombic Pnma a=1657.3 b=12.037 c=4.39484 [8][4]
Sr[B3O(SO4)4(SO4H)] 617.36 monoclinic P21/c a = 11.3309, b= 7.1482, c = 19.355, β = 106.878°, Z = 4 1500.1 2.73 colourless; Sr in 9 coordination by sulfate oxygens [22]
Y2[B2(SO4)6] monoclinic C2/c a=13.5172 b=11.3941 c=10.8994 β=93.447 cyclic [14][4]
Ag[B(SO4)2] P4/ncc a=8.6679 c=7.2897 [4]
Ag[B(S2O7)2] monoclinic P21/c a = 9.507, b = 9.601, c = 11.730, β = 98.35° Z=4 1059.3 2.953 colourless [23]
Cd[B2(SO4)4] [24]
Cd[B2O(SO4)3] 438.20 orthorhombic Pnma a=8.9692 b=11.520 c=8.7275 Z=4 901.8 3.23 colourless [24]
Cd4[B2O(SO4)6] trigonal P3 a=8.2222 c=7.9788 Z=1 467.14 3.78 colourless [24]
(I4)[B(S2O7)2]2 triclinic P1 a = 11.3714 b = 11.5509 c = 12.7811 α = 68.638° β = 68.275° γ = 64.626° Z=2 1366.16 2.999 orange-brown [25]
Cs2B4SO10 501.12 monoclinic C2 a=11.4012 b=6.5997 c=13.5702 β=103.934° Z=4 919.04 3.359 colourless [17]
Cs2[B2O(SO4)3] monoclinic P2/c a=14.765 b=6.710 c=12.528 β=104.50 [20]
Cs3HB4S2O14 P63/m a = 6.5648, c = 19.5669 Z=2 [20]
Cs[B(SO4)(S2O7)] monoclinic P21/c a=10.4525, b=11.319, c=8.2760; β=103.206; Z=4 [8][9]
Cs3Li2[B(SO4)4] monoclinic P21/n a=13.7698 c=8.2376 c=13.9066 β=91.778 [14][4]
Cs3Na2[B(SO4)4] monoclinic P21/c a=13.6406 b=7.9475 c=13.9573 β=990.781 [14][4]
CsK4[B(SO4)4] P43212 a=9.9433 c=16.881 [14][4]
Ba[B2(SO4)4] orthorhombic Pnna a = 12.791, b = 12.800, c = 7.317 Z = 4 [8][26]
Ba[B2O(SO4)3] orthorhombic Pnma a=17.1848 b=12.3805 c=4.4226 [8]
Ba[B(S2O7)2]2 monoclinic I2/a a = 11.6077, b = 8.9144, c = 21.303, β = 104.034° Z = 4 chains [8][26]
La2[B2(SO4)6] monoclinic C2/c a=1379.2 b=1158.9 c=1139.5 β=93.611 cyclic [14][4]
Ce2[B2(SO4)6] monoclinic C2/c 13.740 b=11.5371 c=11.3057 β=93.661 cyclic [14][4]
Pr2[B2(SO4)6] monoclinic C2/c a=13.711 b=11.5305 c=11.2643 β=93.668 cyclic [14][4]
Nd2[B2(SO4)6] monoclinic C2/c a=13.6775 b=11.51.34 11.2046 β=93.5909 cyclic [14][4]
Sm2[B2(SO4)6] monoclinic C2/c a=13.633 b=11.492 c=11.112 β=93.567 cyclic [14][4]
Eu2[B2(SO4)6] monoclinic C2/c a=13.602 b=11.470 c=11.050 β=93.465 cyclic [14][4]
Gd2[B2(SO4)6] monoclinic C2/c a=13.5697 b=11.4426 c=11.0271 β= cyclic [14][4]
Tb2[B2(SO4)6] monoclinic C2/c a=13.5601 b=11.42.48 c=10.9881 β=93.534 cyclic [14][4]
Dy2[B2(SO4)6] monoclinic C2/c a=13.568 b=11.425 c=10.9703 β=93.540 cyclic [14][4]
Ho2[B2(SO4)6] monoclinic C2/c a=13.505 b=11.409 c=10.921 β=93.453 cyclic [14][4]
Er2[B2(SO4)6] monoclinic C2/c a=13.551 b=11.411 c=10.882 β=93.41 cyclic [14][4]
Tm2[B2(SO4)6] monoclinic C2/c a=13.4981 b=11.3617 10.8327 β=93.4500 cyclic [14][4]
Yb2[B2(SO4)6] monoclinic C2/c a=13.495 b=11.3452 c=10.7961 β=93.390 cyclic [14][4]
Lu2[B2(SO4)6] monoclinic C2/c a=13.469 b=11.364 c=10.799 β=93.369 cyclic [14][4]
Pb[B2(SO4)4] 613.05 orthorhombic Pnna a=12.516 b=12.521 c=7.302 Z=4 114.43 3.558 loop chain [4][27]
Pb[B2O(SO4)3] orthorhombic P21/m a=4.4000 b=12.1019 c=8.6043 [4]
Bi2[B2(SO4)6] 659.08 orthorhombic C2/c a = 13.568, b = 11.490, c = 11.106 Z=4 1728.8 3.894 [14]
(H3O)Bi[B(SO4)2]4 1039.72 I4 a=11.857, c=8.149 Z=2 1156.84 2.99 colourless; non-linear optical [14]
(UO2)[B(SO4)2(SO3OH)] 569.52 triclinic P1 a=5.448 b=7.021 c=13.522 α =92.248° β =95.347° γ =101.987° Z=2 3.762 green [28]
(UO2)2[B2O(SO4)3(SO3OH)2] 1058.23 monoclinic P21/n a=10.872 b=11.383 c=14.812 β=92.481 Z=4 3.838 yellow [28]

References

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  26. ^ a b Netzsch, Philip; Pielnhofer, Florian; Höppe, Henning A. (2020-10-19). "From S–O–S to B–O–S to B–O–B Bridges: Ba[B(S 2 O 7 ) 2 ] 2 as a Model System for the Structural Diversity in Borosulfate Chemistry". Inorganic Chemistry. 59 (20): 15180–15188. doi:10.1021/acs.inorgchem.0c02156. ISSN 0020-1669. PMID 33001636. S2CID 222145994.
  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. ^ a b 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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