4-(Tetrahydro-4H-thiopyran-1-oxide-4-ylidene)-cyclohexanone oxime in the solid-state. A two-dimensional network of enantiomorphous chains interconnected by weak hydrogen bonds.

نویسندگان

  • Albert W Marsman
  • Bart L A van Poecke
  • Leonardus W Jenneskens
  • Anthony L Spek
  • Egbertus T G Lutz
  • Joop H van der Maas
چکیده

From a saturated C6H6 solution of racemic 4-(tetrahydro-4H-thiopyran-1-oxide-4-ylidene)-cyclohexanone oxime [1(1-R/1-S)] the co-crystal is crystallized. Single crystal X-ray analysis showed that (1)4.C6H6 (P1 space group) in the solid-state consists of enantiomorphous, non-covalent polymer-like chains that contain, in an alternating fashion, the crystallographically independent enantiomers 1-R and 1-R' or 1-S and 1-S'', respectively. Within each chain the enantiomers are linked by 'head-to-tail' intermolecular oxime-sulfoxide hydrogen bonding [D(2) motif]. Neighbouring chains consist of enantiomers with opposite configuration and possess opposite molecular 'head-to-tail' alignments. The enantiomorphous chains are interconnected by weak intermolecular C-HO hydrogen bonds involving centrosymmetric C-Hoxime [R(12)] and C-Hsulfoxide [R(8)] motifs between the 1-R and 1-S molecules in neighbouring chains; a nearly planar two-dimensional hydrogen bonding network motif is obtained. In the crystallographic direction [1 0 0] the layers stack in such a fashion that chains occupying successive layers with an identical 'head-to-tail' alignment are positioned on top of each other. Concomitantly, channels with areas of ca. 25 Angstroms(2) are obtained, which are occupied by C6H6 solvent molecules. A comparison of the IR and Raman spectra of with those obtained for native 1 that does not contain C6H6, indicates that intermolecular oxime-sulfoxide hydrogen bonding [D(2) motif] also occurs for native 1 in the solid-state.

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عنوان ژورنال:
  • Organic & biomolecular chemistry

دوره 3 8  شماره 

صفحات  -

تاریخ انتشار 2005