Redetermination of the Crystal and Molecular Structure of Cyclohexasulfur, S<sub>6</sub> [1]

Steidel, Jürgen; Pickardt, Joachim; Steudel, Ralf

doi:10.1515/znb-1978-1238

Cited by 79 publications

(46 citation statements)

References 5 publications

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“…The S-S bonds in the Cp2MS5 molecules, with the exception of the short S2-S3 bonds, are all longer than those found in Rb2S5. Cyclohexasulfur, S6, crystallizes in the chair ~onformation with all S-S bond lengths equal at 2.068(2) A (17). This distance is m!rginally greater than the average S-S distances of 2.060 A for 1, Clearly the structures of 1 , 2 , and 3 are quite similar with any significant differences being attributed to differences in the size of the metal atoms.…”

Section: Resultsmentioning

confidence: 94%

Metallacyclohexasulfanes: the crystal and molecular structures of (η⁵-C₅H₅)₂MS₅, M = Zr and Hf

Shaver¹,

McCall²,

Day³

et al. 1987

Can. J. Chem.

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ALAN SHAVER, JAMES M. MCCALL, VICTOR W. DAY, and SARAH VOLLMER. Can. J . Chem. 65, 1676Chem. 65, (1987.The crystal and molecular structures of ( T~~-C~H~)~Z~S~, 2, and ( q 5 -C 5~5 )~f S 5 , 3, have been determined by single crystal diffractometry methods. Both compounds crystallized with four molecules in a monoclinic unit cell of dimensions: a = 8.984(3)A, b = 13.336(4)A,c = 11.421(2)A, P = 93.10(2)"for2, and a = 9.012(2)A, b = 13.291(2)A, c = 11.381(2) A, p = 93.25(1)" for 3; the space group is P21 /n for both. These crystals of 2 and3 are thus isomorphous with those of (CSH5)2TiS5, 1, studied by Epstein et al. (3a). The structures of all three complexes are very similar consisting of a cyclohexane-like six-membered MS5 ring with two C5H5 rings attached to the metals in an axial and equatorial position. The coordination spheres of 2 and 3 are less crowded than that of 1. The consequences of this are discussed with respect to the barriers to ring inversion in these complexes. Introduction Recently a general method for the preparation of metallacyclosulfanes (i.e. species of the type MS,) was reported (1). Treatment of the appropriate dichloro precursors with nonaqueous solutions of Li2S,, prepared in situ, gave the series Cp2MS5 and C P *~M S~, where M = Ti, Zr, and Hf, Cp = C5H5, and Cp* = C5Me5. The complex Cp2TiS5, 1, had been reported previously (2) and had been shown (3) to have a cyclohexanelike six-membered ring with axial and equatorial Cp rings. At room temperature ring inversion is slow on the nrnr time scale for the titanium complex (4); however, only upon cooling the

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Section: Resultsmentioning

confidence: 94%

Metallacyclohexasulfanes: the crystal and molecular structures of (η⁵-C₅H₅)₂MS₅, M = Zr and Hf

Shaver¹,

McCall²,

Day³

et al. 1987

Can. J. Chem.

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“…For example, the ionization energy of cyclo-S 6 of 9.00 eV [7] (t = 73.88 [8] ) is slightly smaller than that of cyclo-S 8 (9.04 eV; [7] t = 98.58 [9] ). In cyclo-S 7 one torsion angle has the value 08 [10] resulting in a considerably lower ionization energy of 8.67 eV.…”

Section: Abstract: Complex Formation Between Gaseous LImentioning

confidence: 93%

“…[11] The interaction of metal cations with neutral sulfur molecules S n is very weak and only a few solid coordination compounds are known in which sulfur molecules function as neutral ligands. Examples are several silver salts with the cations [AgS 8 ]…”

Section: Abstract: Complex Formation Between Gaseous LImentioning

confidence: 99%

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Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Steudel

Wong

Steudel

2005

Chemistry A European J

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Complex formation between gaseous Li+ ions and sulfur-containing neutral ligands, such as H2S, Me2Sn (n = 1-5; Me = CH3) and various isomers of hexasulfur (S6), has been studied by ab initio MO calculations at the G3X(MP2) level of theory. Generally, the formation of LiS(n) heterocycles and clusters is preferred in these reactions. The binding energies of the cation in the 29 complexes investigated range from -88 kJ mol(-1) for [H2SLi]+ to -189 kJ mol(-1) for the most stable isomer of [Me2S5Li]+ which contains three-coordinate Li+. Of the various S6 ligands (chair, boat, prism, branched ring, and triplet chain structures), two isomeric complexes containing the S5==S ligand have the highest binding energies (-163+/-1 kJ mol(-1)). However, the global minimum structure of [LiS6]+ is of C(3v) symmetry with the six-membered S(6) homocycle in the well-known chair conformation and three Li--S bonds with a length of 256 pm (binding energy: -134 kJ mol(-1)). Relatively unstable isomers of S6 are stabilized by complex formation with Li+. The interaction between the cation and the S6 ligands is mainly attributed to ion-dipole attraction with a little charge transfer, except in cations containing the six sulfur atoms in the form of separated neutral S2, S3, or S4 units, as in [Li(S3)2]+ and [Li(S2)(S4)]+. In the two most stable isomers of the [LiS6]+ complexes, the number of S--S bonds is at maximum and the coordination number of Li+ is either 3 or 4. A topological analysis of all investigated complexes revealed that the Li--S bonds of lengths below 280 pm are characterized by a maximum electron-density path and closed-shell interaction.

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“…Derartige, unter speziellen Bedingungen gezüchtete Kristalle ergaben bei Röntgenbeugungs-untersuchungen die Raumgruppe R3 mit den Gitterkonstanten a = 1140 und c = 447 pm [16]. In der gleichen Raumgruppe kristallisiert Se [17], so daß es sich bei den Stäbchen möglicherweise um See handelt, zumal das Achsenverhältnis c\a in beiden Fällen gleich ist. Eine nähere Untersuchung ist im Gange.…”

Section: Introductionunclassified

Nachweis von Se₆, Se₇ und Se₈ in Lösungen yon Selen mittels Hochdruckflüssigkeitschromatographie / Detection, of Se₆, Se₇ and Se₈ in Selenium Solutions by High-Pressure Liquid Chromatography

1981

Zeitschrift Für Naturforschung B

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Abstract Dissolution of crystalline Se8 or extraction of glassy or red amorphous selenium, prepared from aqueous SeO2 by reduction, by organic solvents yields solutions containing Se6, Se7 and Se8 in equilibrium as shown by HPLC. The equilibrium explains the concentration dependence of the molar absorbance of such solutions observed earlier. Since the Raman spectrum of red amorphous selenium does not show any lines due to Se6 Se7 and Se8 a rapid interconversion of selenium molecules in solution at 20 °C is postulated. Red amorphous selenium may consist of a mixture of small and medium sized ring molecules

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Redetermination of the Crystal and Molecular Structure of Cyclohexasulfur, S₆ [1]

Abstract: A low temperature (-90 °C) X-ray structural analysis of S6 single crystals yielded improved data for the bond distances (206.8 pm), bond angles (102.6°), and torsion angles (73.8°) of the D3d molecule which are in agreement with current theories of homonuclear sulfur bonds.

Cited by 79 publications

References 5 publications

Metallacyclohexasulfanes: the crystal and molecular structures of (η⁵-C₅H₅)₂MS₅, M = Zr and Hf

Metallacyclohexasulfanes: the crystal and molecular structures of (η⁵-C₅H₅)₂MS₅, M = Zr and Hf

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Nachweis von Se₆, Se₇ und Se₈ in Lösungen yon Selen mittels Hochdruckflüssigkeitschromatographie / Detection, of Se₆, Se₇ and Se₈ in Selenium Solutions by High-Pressure Liquid Chromatography

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Redetermination of the Crystal and Molecular Structure of Cyclohexasulfur, S6 [1]

Abstract: A low temperature (-90 °C) X-ray structural analysis of S6 single crystals yielded improved data for the bond distances (206.8 pm), bond angles (102.6°), and torsion angles (73.8°) of the D3d molecule which are in agreement with current theories of homonuclear sulfur bonds.

Cited by 79 publications

References 5 publications

Metallacyclohexasulfanes: the crystal and molecular structures of (η5-C5H5)2MS5, M = Zr and Hf

Metallacyclohexasulfanes: the crystal and molecular structures of (η5-C5H5)2MS5, M = Zr and Hf

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Nachweis von Se6, Se7 und Se8 in Lösungen yon Selen mittels Hochdruckflüssigkeitschromatographie / Detection, of Se6, Se7 and Se8 in Selenium Solutions by High-Pressure Liquid Chromatography

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Redetermination of the Crystal and Molecular Structure of Cyclohexasulfur, S₆ [1]

Metallacyclohexasulfanes: the crystal and molecular structures of (η⁵-C₅H₅)₂MS₅, M = Zr and Hf

Metallacyclohexasulfanes: the crystal and molecular structures of (η⁵-C₅H₅)₂MS₅, M = Zr and Hf

Nachweis von Se₆, Se₇ und Se₈ in Lösungen yon Selen mittels Hochdruckflüssigkeitschromatographie / Detection, of Se₆, Se₇ and Se₈ in Selenium Solutions by High-Pressure Liquid Chromatography