(IUCr) A 3,5-dinitrobenzoyl derivative of a stereoisomer of glycerol menthonide

Volume 65
Part 7
Page o1540
July 2009

Received 19 May 2009
Accepted 3 June 2009
Online 10 June 2009

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R = 0.018
wR = 0.045
Data-to-parameter ratio = 11.9
Details

A 3,5-dinitrobenzoyl derivative of a stereoisomer of glycerol menthonide

Anthony Kiessling,^a ^* Charles Campana ^b and Margaret E. Kastner ^c

^aDepartment of Chemistry and Physics, Mansfield University, Mansfield, PA 16933, USA,^bSenior Scientist, Single CrystalDiffraction, Bruker AXS Inc., 5465 East Cheryl Parkway, Madison, WI 53711-5373, USA, and ^cDepartment of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
Correspondence e-mail: akiessli@mansfield.edu

The title compound, [(2S,5R,6S,9R)-6-isopropyl-9-methyl-1,4-dioxaspiro[4.5]dec-2-yl]methyl 3,5-dinitrobenzoate, C₂₀H₂₆N₂O₈, was synthesized as part of a study of three-carbon stereochemical systems. The crystallographic assignment of the absolute stereochemistry is consistent with having started with (-)-menthone, the acetal carbon is R and the secondary alcohol is S. This brings the dinitrobenzoate into approximately the same plane as the menthyl ring and anti to the isopropyl group. Close intermolecular C=ONO₂ contacts between neighboring molecules [2.8341 (16) Å] contribute to the packing arrangement. The structure was refined as a pseudo-merohedral twin (monoclinic space group P2₁ emulating the orthorhombic space group C222₁). Application of the twin law 100, 0 $[\overline{1}]$ 0, $[\overline{1}]$ 0 $[\overline{1}]$ gave a 2:1 ratio of twin moieties [refined BASF value = 0.3790 (7)].

Related literature

For the synthesis of glycerol menthonide, see: Greenberg (1999). For the synthesis and NMR spectra of the title compound, see: Kiessling et al. (2009). Glidewell et al. (2003) report a related structure with a very short C=O NO₂ distance. Allen et al. (1998) discuss intermolecular C=O C=O interactions. For a description of the Cambridge Crystallographic Database, see: Allen (2002).

Experimental

Crystal data

C₂₀H₂₆N₂O₈
M_r = 422.43
Monoclinic, P 2₁
a = 9.4396 (5) Å
b = 5.8825 (3) Å
c = 19.6719 (10) Å
= 103.923 (3)°
V = 1060.26 (9) Å³
Z = 2
Cu K radiation
= 0.87 mm^-1
T = 100 K
0.38 × 0.09 × 0.02 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008) T_min = 0.602, T_max = 0.977
16481 measured reflections
3275 independent reflections
3254 reflections with I > 2(I)
R_int = 0.025

Refinement

R[F² > 2(F²)] = 0.018
wR(F²) = 0.045
S = 1.06
3275 reflections
276 parameters
1 restraint
H-atom parameters constrained
_max = 0.10 e Å^-3
_min = -0.11 e Å^-3
Absolute structure: Flack (1983), 1131 Friedel pairs
Flack parameter: 0.03 (13)

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2211 ).

Acknowledgements

We would like to thank the Mansfield University Foundation for supporting this research.

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta Cryst. B54, 320-329.
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Winsonsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2003). Acta Cryst. C59, o144-o146.
Greenberg, M. (1999). US Patent No. 5 977 166.
Kiessling, A., Ganong, C. & Johnson, A. (2009). Am. J. Undergrad. Res. 8, 1-6.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.

organic compounds