Allotropes of sulfur

The element sulfur exists as many allotropes. In number of allotropes, sulfur is second only to carbon.^[1] In addition to the allotropes, each allotrope often exists in polymorphs (different crystal structures of the same covalently bonded S_n molecules) delineated by Greek prefixes (α, β, etc.).^[2]

Furthermore, because elemental sulfur has been an item of commerce for centuries, its various forms are given traditional names. Early workers identified some forms that have later proved to be single or mixtures of allotropes. Some forms have been named for their appearance, e.g. "mother of pearl sulfur", or alternatively named for a chemist who was pre-eminent in identifying them, e.g. "Muthmann's sulfur I" or "Engel's sulfur".^[2][3]

The most commonly encountered form of sulfur is the orthorhombic polymorph of S₈, which adopts a puckered ring – or "crown" – structure. Two other polymorphs are known, also with nearly identical molecular structures.^[4] In addition to S₈, sulfur rings of 6, 7, 9–15, 18, and 20 atoms are known.^[5] At least five allotropes are uniquely formed at high pressures, two of which are metallic.^[6]

The number of sulfur allotropes reflects the relatively strong S−S bond of 265 kJ/mol.^[1] Furthermore, unlike most elements, the allotropes of sulfur can be manipulated in solutions of organic solvents and are analysed by HPLC.^[7]