Polyatomic cations of sulfur. II. Crystal structure of octasulfur bis(hexafluoroarsenate), S8(AsF6)2

Abstract

gen atoms. In fact, the hole size (the approximate radius is 3.5 Á taking phenyl hydrogens into account) seems large enough to accommodate larger anions. Thus, the structure of the trifluoroaCetonitrile adduct of Cu2 (Ns)2 ((CH2P(C6Hs)2)2)3,28 which is currently under investigation, might be expected to have a similar overall geometry.

X-ray study of structure and charge density of 1-methylsulfonyl-2-phenylsulfonylethane

“…Slight changes in the ring electron density furthermore can have a drastic effect on the spatial structures of cyclic S and SN compounds. This is amply illustrated in the series S 8 --, S~ + --, S4N 4 (isoelectronic with Sg +) --, 54 N2+ where the number of n electrons decreases by 2 in each successive member (Davies et al, 1971;Gillespie, Slim & Tyrer, 1977).…”

“…The shortest transannular S--.S contacts in these molecules are in the range 3.20-3.35A, corresponding to short van der Waals distances. In the cyclic ion S 2+, however, there are three short transannular S... S contacts, 2.86-3.00/~, implying partial bonding (Davies, Gillespie, Park & Passmore, 1971).…”

The Nature of Transannular Interactions in E4N4 and E82+ (E = S, Se)

“…7,8 For S8 2+ , the high-resolution X-ray structure of the salt S8(AsF6)2 by Passmore et al is used as a reference, 19 while the optimized metrical parameters of Se8 2+ are compared with data for the dication in the salt (Te6 4+ )(Se8 2+ )(AsF6 -)6(SO2) as determined by Gillespie et al 17 In the crystallographic data, tetrachalcogen tetranitrides and octachalcogen dications have nearly ideal D2d and Cs molecular symmetries, respectively. 4,5,7,8,15,19 For E4N4, there are several short (3.1 -3.2 Å) E⋯N contacts between the four molecules in the unit cell. Similarly, short (2.7 -3.3 Å) E⋯F contacts exist between the chalcogen dications and AsF6 -anions in the X-ray data of both S8 2+ and Se8 2+ .…”

“…The homopolyatomic chalcogen dications E8 2+ (4ac) (E = S, Se, Te) are also structurally related to the eight-membered chalcogennitrogen rings, but the presence of two more valence electrons compared to 1 gives them an overall chair-like molecular shape with only one weak cross-ring E⋯E contact. [15][16][17][18][19] The nature of transannular interactions in 14 has been a matter of much debate ever since the solid state structure of S4N4 was first reported. 14, A simple way to rationalize the cage-like structure of S4N4 using molecular orbitals from extended Hückel calculations was presented by Gleiter as early as in 1970.…”

Uber die Reaktionen von Molekülen (R2CS)2 (R = CF3, CI) und Cl2CS mit XeF+MF6 - (M = As, Sb) und Kristallstruktur von [1] / On the Reactions of Molecules (R2CS)2 (R = CF3, Cl) and Cl2CS with XeF+MF6 - (M = As, Sb) and Crystal Structure of (CF3) [1]

“…Im Vergleich dazu b e trägt d e r ringüberbrückende A bstand S -S im S82+-K ation 2,86 A , was ein er Teilbindung e n t spricht, die zu den übrigen SS-B indungen jr-Chara k te r besitzt [30]. …”