The crystal and molecular structure of syn-9-phenyl-2,11-dithia[3,3]metacyclophane

Abstract

. Can. J. Chem. 62, 661 (1984).The crystal structure of syn-9-phenyl-2,11-dithia[3,3]metacyclophane, 6, has been determined by single crystal X-ray diffraction an{ refined to an R value of 0.0723. ' The crystal structure is triclinic with a_ = 9.573(2), b = 12.010(4), c = 8.433(2) A, a = 108.02(2)", P = 95.95(2)", y = 102.25(3)", and the space group is PI with two molecules per cell, D,,,,,, = 1.3 13 g cm-', D,,,,,, = 1.306 g cm-'. The bridging S atoms differ in their conformations so that the S . . . S distance is 6.391 A. The metacyclophane rings have a distance of 3.57 A between their centres and form a dihedral angle of 20.5".The phenyl substituent forms an angle of 78.6" with the adjacent ring and has an ortho H-atom very close to the internal H-atom of the opposite ring. The phenyl substituted aromatic ring is non-planar and in a shallow boat form, the ring atoms C(l I) (internal) and C(14) being 0.038(4) and 0.037(5) A out-of-plane on the outside, the methylene C substituents are 0.212(5) and 0.199(5) A out-of-plane on the inside. The first atom of the phenyl group is in the bowsprit position and is 0.274(4) A above the mean plane on the outer side of the molecule. Tht opposite metacyclophane ring is less strained but in a similar boat form with the methylene C-atoms 0.092(4) and 0.067(6) A to the inside. The mean bond angle at S is 103.5(2)", the angles at C (methylene) range from 113.3(3)" to 118.0(3)".The variable temperature 'Hmr spectra results are consistent with the syn conformer 6 being dominant in solution and frozen at temperatures <60°C as conformer A, with only relatively restricted further twisting of the biphenyl being found at ambient temperature.WILLEM ANKER, KATHY A. BEVERIDGE, GORDON W. BUSHNELL et REGINALD H. MITCHELL. Can. J. Chem. 62,661 (1984). On a dtterminC la structure cristalline du phCnyl-9 dithia-2,ll [3,3]mCtacyclophane-sy, 6, par diffraction de rayons-X sur un cristal unique et on I'affinCe jusqu'a une valeur de R de 0,0723. La structure cristalline est triclinique avec a = 9,573(2), Les spectres de rmn du proton a tempkrature variable sont en accord avec l'hypothkse que la conformation syn (6) est prepondkrante en solution et qu'a des tempkratures <6OoC, le produit est fig6 sous la conformation A alors que l'on ne peut observer que des variations relativement faibles du biphCnyle a la temperature ambiante.[Traduit par le journa)]

Synthesis, Complexation, and Supramolecular Assembly of 21,30-Dithia-17,25-dimethyl-1,4,7,10,13- pentaoxa[13.3.3](1,2,6)cyclophane

“…In another example, a crownophane prepared by a tandem Claisen rearrangement could capture a water molecule via multiple hydrogen bonds . Dithia[3.3]metacyclophane is an important member of the cyclophane family as it can undergo interesting aromatic ring-tilting and bridge-flipping processes. − If it is incorporated into a crownophane, the cavity size of the crown moiety may be to some extent varied by the tilting of the two aromatic rings, while the mobility of the thia-bridges may also have an effect on its complexation behavior. This paper thus describes the preparation, complexation behavior, and molecular structure of a dithia[3.3]metacyclophane-based crownophane.…”

Generation and NMR studies of stable cations derived from monothia[3.2]- and dithia[3.3]metacyclophanes

“…1,2 They have also received considerable attention for their conformational behavior and NMR properties as a function of intra-annular substitution and other structural variations. [3][4][5][6][7][8][9] The dithia [3.3]phane route has become a standard protocol for the synthesis of [2.2]cyclophanes and cyclophane-dienes via the Stevens rearrangement-Hoffmann elimination sequence, in which the bis(sulfonium) salts are the key intermediates. 8 Monothia[3.2]cyclophanes are intermediates in the synthesis of [2.2]metacyclophane-monoenes whose chemistry is just beginning to be unravelled.…”

Synthesis and Structural Study of Thiacyclophanes Utilizing Dibromides and Methane Dithiolate

“…Thiacyclophanes are important members in the cyclophane family since they can undergo functional group transformations, interesting aromatic ring-tilting, and bridge-flipping processes. − Macrocyclic crownophanes are important for creating highly organized linear supramolecular assembly and neutral ditopic super structures . Herz has reported a series of diastereomeric paracyclophanes by a coupling reaction of suitable dibromide and dithiol.…”