Thiabowls:  Synthesis, Molecular Structure, and Novel Supramolecular Architecture of Trithia-[3]-Peristylane

Abstract

A synthesis of trithia-[3]-peristylane, C(6)H(6)S(3), a novel C(3)(v)() symmetric thiabowl, from the exotic hydrocarbon bullvalene has been accomplished. The X-ray crystal structure of this trithiabowl displays an unprecedented supramolecular architecture in the solid state with 12 CH.S interactions involving all of its six hydrogen atoms and the two lone pairs on each of the three sulfur atoms.

Self-Assembly of Mercaptane−Metallacarborane Complexes by an Unconventional Cooperative Effect: A C−H···S−H···H−B Hydrogen/Dihydrogen Bond Interaction

“…In addition to the previous SH···(HB) 2 DHB interaction in compound 1 , the SH group is also involved in another classical C−H···S hydrogen bond interaction. The observed C c 2 −H 2 ···S 1 distance of 2.628 Å is substantially shorter than the 3.0 Å distance corresponding to the sum of the van der Waals radii of hydrogen and sulfur atoms (Table , entry 1), and the near-linear C c −H···S angle (151.49°) qualifies it to be a hydrogen bond (between units A and B in Figures and ). , Another longer and nondirectional contact is also seen in the structure (between molecules B and C), C c 1 −H 1 ···S 1 (2.872 Å, 125.73°), so that it is probably less attractive and consequently contributes less to the crystal packing effects. , Experimental evidence for the presence of these bonding interactions in the solid state is obtained from the solid-state infrared spectra of 1 . The IR spectrum of 1 in KBr exhibits two stretching frequencies for carborane C c −H (3074 and 3047 cm -1 ), whereas only one C c −H band is observed experimentally for closo -[3-Ru(η 6 -C 6 H 6 )-1,2-C 2 B 9 H 11 ] ( 2 ) (3073 cm -1 ), which is the result of substituting the SH group in 1 by a H atom .…”

From Noncovalent Chalcogen–Chalcogen Interactions to Supramolecular Aggregates: Experiments and Calculations

“…The C–H···π distances recorded for these two ring systems (2.85 and 2.89 Å) compare well with other weak hydrogen bonds. − ,, The comparison of the data listed in Table reveals that the contributions of the E···E interactions increase in the sequence S-Se-Te, whereas the other weak interactions decrease from S to Se and Te. A comparison of the C–H···S and S···S bond lengths in Table , respectively, reveals very similar distances as reported for the thiabowls trithia-[3]-peristylane: C–H···S = 3.05 and 3.09 Å and tetrathia-[4]-peristylane: C–H···S = 2.93 Å and S···S = 3.61 Å. , …”

[n]Imperilenes: Stacked [n]Trannulenes Separated by Planar Cycloalkane Rings

“…In 1986, McEwen and Schleyer considered unsaturated peristylapolyenes, with conjugated double bonds introduced around their perimeters, 7 in their theoretical examination of molecules exhibiting "in-plane aromaticity." They found that such [3]-and [5]-peristylenes (with 4n þ 2 π electrons) were aromatic but the 4n π electron [4]-peristylene was antiaromatic.…”

“…Eaton et al’s successful synthesis in 1972 of a dodecahedrane fragment made up of six fused pentagons, “[5]-peristylane” (Figure ), introduced a new family of polycyclic hydrocarbons. This has been augmented by the preparation of [3]- and [4]-peristylanes − as well as several aza, oxa, and thio heteroperistylanes …”