Borosulfate

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

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

	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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