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Top Curr Chem (2003) 230:1–79 DOI 10.1007/b12110 Solid Sulfur Allotropes Ralf Steudel1 · Bodo Eckert2 1 Institut für Chemie, Sekr. C2, Technische Universität Berlin, 10623 Berlin, Germany E-mail: steudel@schwefel.chem.tu-berlin.de 2 Fachbereich Physik, Universität Kaiserslautern, 67663 Kaiserslautern, Germany E-mail: eckert@physik.uni-kl.de Abstract Sulfur is the element with the largest number of solid allotropes. Most of these con- sist of unbranched cyclic molecules with ring sizes ranging from 6 to 20. In addition, poly- meric allotropes are known which are believed to consist of chains in a random coil or heli- cal conformation. Furthermore, several high-pressure allotropes have been characterized. In this chapter the preparation, crystal structures, physical properties and analysis of these allotropes are discussed. Ab initio MO calculations revealed the existence of isomeric sulfur rings with partly rather unusual structures at high temperatures. Keywords Sulfur homocycles · Sulfur chains · Polymerization · Physical properties · High-pressure allotropes · Crystal structures 1 Introduction................................ 3 2 AllotropesatAmbientPressure.................... 4 2.1 Preparation................................. 4 2.1.1 AllotropesConsistingofCyclicMolecules . . . . . . . . . . . . . 4 2.1.1.1 PreparationofS6.............................. 4 2.1.1.2 PreparationofS7.............................. 6 2.1.1.3 PreparationofPureS8 .......................... 6 2.1.1.4 PreparationofS9.............................. 8 2.1.1.5 PreparationofS10 ............................. 8 2.1.1.6 PreparationofS6·S10 ........................... 9 2.1.1.7 PreparationofS11 ............................. 9 2.1.1.8 PreparationofS12 ............................. 10 2.1.1.9 PreparationofS13 ............................. 11 2.1.1.10 PreparationofS14 ............................. 12 2.1.1.11 PreparationofS15 ............................. 12 2.1.1.12 PreparationofS18 ............................. 13 2.1.1.13 PreparationofS20 ............................. 13 2.1.2 Allotropes Consisting of Long Sulfur Chains (PolymericSulfur:Sm,SyandSw)................... 14 2.2 MolecularandCrystalStructures................... 16 2.2.1 AllotropesConsistingofCyclicMolecules . . . . . . . . . . . . . 17 2.2.1.1 RhombohedralS6 ............................. 17 2.2.1.2 AllotropesofS7............................... 19 2.2.1.3 AllotropesofS8............................... 21 2.2.1.3.1 Orthorhombica-S8 ............................ 24 Springer-Verlag Berlin Heidelberg 2003PDF Image | Topics in Current Chemistry
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