Synthesis and Characterization of the Trisulfate Pb[S3O10] and Theoretical Analysis of H2S3O10

被引：19

作者：

Logemann, Christian ^{[1
]}

Kluener, Thorsten ^{[1
]}

Wickleder, Mathias S. ^{[1
]}

机构：

[1] Carl von Ossietzky Univ Oldenburg, Inst Pure & Appl Chem, D-26129 Oldenburg, Germany

来源：

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2012年 / 638卷 / 05期

关键词：

Trisulfate; Lead; X-ray diffraction; Thermal behavior; Calculations; CRYSTAL-STRUCTURE; LONE-PAIR; PHASE; TEMPERATURE; DIFFRACTION; REFINEMENTS; POWDER; ORIGIN; PBO;

D O I：

10.1002/zaac.201100533

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of (NH4)2PbCl6 and fuming sulfuric acid (65?% SO3) in a sealed glass tube at 250 degrees C led to colorless single crystals of Pb[S3O10] (orthorhombic, Pbcn, Z = 4, a = 10.9908(4), b = 8.5549(3), c = 8.0130(3) angstrom, V = 753.42(5) angstrom 3). The compound shows a three-dimensional linkage of the tenfold oxygen coordinated Pb2+ ions and exhibits the unusual trisulfate anion, [S3O10]2, that consists of three vertex connected [SO4] tetrahedra. The distances SO within the SOS bridges of the anion are remarkable asymmetric with distances of 155 and 169 pm, respectively. This structural feature is well reproduced by calculations on a PBE0/cc-pVTZ and a MP2/cc-pVTZ level of theory. Similar calculations allow also for an inspection of the yet unknown corresponding acid, H2S3O10. Also for this acid non-symmetric SOS bridges are predicted. The thermal behavior of Pb[S3O10] is characterized by the loss of two equivalents of SO3 at low temperature and the decomposition of intermediate Pb[SO4] at higher temperature.

引用

页码：758 / 762

页数：5

共 46 条

[1] SIMPLE CALCULATIONS OF BOND LENGTHS AND BOND ANGLES IN CERTAIN OXIDES, FLUORIDES OR OXIDE FLUORIDES OF SB3+, TE4+ AND PB2+ [J].

ANDERSSON, S ;

ASTROM, A ;

GALY, J ;

MEUNIER, G .

JOURNAL OF SOLID STATE CHEMISTRY, 1973, 6 (02) :187-190

[2]

[Anonymous], 2009, STAR V 9 3

[3]

[Anonymous], OPUS 6 5

[4]

Beck HP, 1999, Z ANORG ALLG CHEM, V625, P1998, DOI 10.1002/(SICI)1521-3749(199912)625:12<1998::AID-ZAAC1998>3.0.CO

[5]

2-U

[6] ReO2Cl(S2O7), a Molecular Disulfate [J].

Betke, Ulf ;

Dononelli, Wilke ;

Kluener, Thorsten ;

Wickleder, Mathias S. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (51) :12361-12363

[7] THE CRYSTAL STRUCTURE OF LANARKITE, PBO.PBSO4 [J].

BINNIE, WP .

ACTA CRYSTALLOGRAPHICA, 1951, 4 (05) :471-472

[8]

Brauer G., 1975, Handbuch der Praparativen Anorganischen Chemie, V3

[9] CRYSTAL STRUCTURE OF TETRASELENIUM BIS(HYDROGEN DISULFATE) [J].

BROWN, ID ;

CRUMP, DB ;

GILLESPI.RJ .

INORGANIC CHEMISTRY, 1971, 10 (10) :2319-&

[10] REFINEMENTS OF STRUCTURES CONTAINING BONDS BETWEEN SI P S OR CL + O OR N .9. (NOPLUS2)2.S3O2MINUS/10 [J].

CRUICKSHANK, DWJ .

ACTA CRYSTALLOGRAPHICA, 1964, 17 (06) :684-&

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