Missing Links in the Sulfate Chemistry of Group 15 Elements: As(S₂O₇)(HS₂O₇), Sb₂(SO₄)₂(S₂O₇), and Bi₂(S₂O₇)₃ from Reactions in Oleum under Harsh Conditions

Abstract

The reactions of As 2 O 3 , SbCl 3 , and (BiO) 2 CO 3 with oleum (65 % SO 3 ) yielded single crystals of As(S 2 O 7 )(HS 2 O 7 ) [monoclinic, P2 1 /c, Z = 4, a = 16.549(1), b = 6.6743(5), c = 9.9498(6) Å, β = 102.672(8)°, V = 1072.672(8) Å 3 ], Sb 2 (SO 4 ) 2 (S 2 O 7 ) [monoclinic, P2 1 /n, Z = 4, a = 9.1586(2), b = 6.9981(2), c = 17.7956(4) Å, β = 100.9690(8)°, V = 1119.73(5) Å 3 ], and Bi 2 (S 2 O 7 ) 3 [triclinic, P1, Z = 2, a = 6.5734(1), b = 10.1954(2), c = 11.5121(2) Å, α = 90.996(1)°, β = 96.976(1)°, γ = 94.870(1)°, V = 762.75(2) Å 3 ]. As(S 2 O 7 )(HS 2 O 7 ) shows the arsenic atoms in a trigonal pyramidal coordination of the * Prof. Dr. M. S. Wickleder

Synthesis, Crystal Structures, and Thermal Analyses of Two New Antimony Tellurite Sulfates: [Sb2(TeO4)](SO4) and [Sb2(TeO3)2](SO4)

“…As trivalent antimony is susceptible to oxidation, a considerably smaller number of Sb(III)-oxy compounds were found as compared to Sb(V)-oxy compounds. For compounds containing Sb(III), the most frequently observed coordination polyhedra are the [ [14] Sb 2 (S 2 O 7 ) 3 , [15] Sb 2 (OH) 2 (SO 4 ) 2 • 2H 2 O, [16] one dimensional chains in Sb 4 O 2 (OH)(SO 4 ) 4 (H 5 O 2 ) • H 2 O, [17] two dimensional layers in CuSb 6 O 8 (SO 4 ) 2 , [18] ASb(SO 4 ) 2 (A = K, Cs), [19] three dimensional framework in Sb 6 O 7 (SO 4 ) 2 , [20,21] Sb 4 O 4 (OH) 2 SO 4 , [22,23] , Sb 2 (SO 4 ) 2 (S 2 O 7 ), [24] RbSbSO 4 Cl 2 , [25] K 4 Sb(SO 4 ) 3 Cl. [26] Various types of linkage among the coordination polyhedra are adopted in these compounds.…”

Dimers and Chains of Hydrogen bonded [HS2O7]– Anions in the Crystal Structures of M[HS2O7] (M = K, [NH4], [NO], Rb, Cs)

“…The most simple hydrogenpolysulfate is [HS 2 O 7 ] – but also for this anion only a limited number of compounds has been reported. These compounds are [NO 2 ][HS 2 O 7 ] that has been presented already in 1954,4 the tetraselenium compound Se 4 [HS 2 O 7 ] 2 described by Gillespie et al5, and, moreover, the complex metallates Ba 2 [Pd(HS 2 O 7 ) 2 (S 3 O 10 ) 2 ]6 and Li 13 [Zr(HS 2 O 7 )(S 2 O 7 ) 3 ] 3 [Zr(S 2 O 7 ) 4 ]7, the unique non‐metal sulfate As[HS 2 O 7 ][S 2 O 7 ]8, and the ferromagnetically ordering palladium hydrogendisulfate Pd[HS 2 O 7 ] 2 9.…”

From Infinite Chains according to1∞[Zr(S2O7)4/2] in Zr(S2O7)2to the unprecedented [Zr(S2O7)4]4-Anion in Ag4[Zr(S2O7)4]

“…Usually the S 2 O 7 2– anion is a strongly linking group and the structures of disulfates show mostly a strong three‐dimensional connectivity. Divergent examples are Te(S 2 O 7 ) 2 , which shows also a chain structure, at least if Te–O contacts of 270 pm and above are taken into account, the layer‐type structure of As(S 2 O 7 )(HS 2 O 7 ), and the molecular structure of ReO 2 Cl 2 (S 2 O 7 ) 2 exhibiting dimers of [ReO 2 Cl 2 (S 2 O 7 )] moieties . Another special case is (IO 2 ) 2 S 2 O 7 , which has been presented by Jansen and co‐workers in 1997 .…”