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Acta Cryst. (2013). E69, o799    [ doi:10.1107/S1600536813011197 ]

(1S,2S,5S)-2-Methyl-3-oxo-5-(prop-1-en-2-yl)cyclohexane-1-carbonitrile

M. L. Rivadulla, A. Fall, M. González and M. J. Matos

Abstract top

The molecule of the title compound, C11H15NO, contains a cyclohexanone ring, three defined stereocenters and an exocyclic double bond. The crystal structure is the result of a study on the Michael addition reaction of (S)-carvone with sodium cyanide using ionic liquids as the reaction medium and so the absolute configuration is known from the chemistry. The six-membered ring is in a chair conformation.

Comment top

Ionic Liquids (ILs) have been attracting considerable attention in the last decade as a new media due to their unique physical and chemical properties (Welton, 1999, Wasserscheid and Keim, 2000). They are often preferred as being more environmentally friendly than traditional organic solvents. The range of known and available ILs has been rapidly growing and nowadays many ILs are commercially available. In accordance with current trends in academic and industrial research, in recent years our research group has also began to work towards the replacement of toxic volatile organic solvents with ILs. In the title compound, I, (Fig. 1), it is observed that the six-membered ring adopts the usual chair conformation. The C1–C2 bond of the cyclohexanone moiety adopts a cis configuration. The dihedral angle between the main plane of the cyclohexanone ring (defined for C1–C3–C4–C6) and the main plane of the lateral chain (defined for C5–C7–C8–C9) is 73.97°. The C5–C7–C8–C9 atoms of the lateral chain are co-planar but show large thermal motion. The absolute configuration was established according to the configuration of the starting material.

Related literature top

For recent review of Ionic liquids as solvents, see: Welton (1999); Wasserscheid & Keim (2000).

Experimental top

Over a stirring solution of (S)-(+)-Carvone (104µL; 0.67 mmol) in the ionic liquid [TMG][LAC] (1 mL), NaCN (39.15 mg; 0.8 mmol) was added. The mixture was stirred at 60 °C for 12 h. Then the reaction was cooled at room temperature and was quenched with water (15 mL) and extracted with AcOEt. The organic layer was washed with a aqueous solution of HCl (10%) (2x10 ml) and brine (2x10 mL), then was concentrated under vacuum and the residue was purified by flash column chromatography on silica gel (5% AcOEt/hexane) to afford the two desired diastereosiomeric compounds (116 mg; 86/14; 99%). The title compound, was crystallized using a mixture of 30% AcOEt/hexane.

Refinement top

In (I) H atoms were placed in calculated positions and treated as ding atoms with C—H(tertiary), 0.98Å, C—H2(secondary), 0.97Å, C C—H2(terminal), 0.93Å, with Uiso = 1.2Ueq(C) and C—H(methyl), 0.96Å, with Uiso =1.5Ueq(C).

The H atoms attached to atom C11 were located on a final difference map. Atoms C8 and C9 show large thermal motion and, as a result, their contact distances to atom C7 are shorter than would be expected. Since the C7—C8 distance was longer than the C7—C9 distance C8 was assumed to be the methyl carbon. The H atoms attached to C8 and C9 could not be clearly seen on a final difference map.

Since no atom in the structure had an atomic number greater than 8 the absolute configuration could not be deterimed with Mokα radiation hence the Flack parameter is meaningless.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2007); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
(1S,2S,5S)-2-Methyl-3-oxo-5-(prop-1-en-2-yl)cyclohexane-1-carbonitrile top
Crystal data top
C11H15NODx = 1.061 Mg m3
Mr = 177.24Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 3155 reflections
a = 5.2892 (8) Åθ = 2.8–26.9°
b = 10.7213 (16) ŵ = 0.07 mm1
c = 19.559 (3) ÅT = 293 K
V = 1109.1 (3) Å3Prism, colourless
Z = 40.60 × 0.56 × 0.42 mm
F(000) = 384
Data collection top
Bruker SMART CCD area-detector
diffractometer
2590 independent reflections
Radiation source: fine-focus sealed tube2112 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
phi and ω scansθmax = 27.9°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1995)
h = 66
Tmin = 0.861, Tmax = 1.000k = 1313
7138 measured reflectionsl = 1925
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.1051P)2 + 0.0575P]
where P = (Fo2 + 2Fc2)/3
2590 reflections(Δ/σ)max < 0.001
120 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C11H15NOV = 1109.1 (3) Å3
Mr = 177.24Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.2892 (8) ŵ = 0.07 mm1
b = 10.7213 (16) ÅT = 293 K
c = 19.559 (3) Å0.60 × 0.56 × 0.42 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2590 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1995)
2112 reflections with I > 2σ(I)
Tmin = 0.861, Tmax = 1.000Rint = 0.023
7138 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.164Δρmax = 0.24 e Å3
S = 1.04Δρmin = 0.20 e Å3
2590 reflectionsAbsolute structure: ?
120 parametersFlack parameter: 1 (2)
0 restraintsRogers parameter: ?
Special details top

Experimental. 1H-NMR (CDCl3, δ): δ(eq) 4.83 (2H, J=26.07 Hz, H-9), 3.35–3.32 (1H, m, H-3), 2.82–2.74 (1H, m, H-5), 2.63–2.55 (2H, m, H-2 + Heq-4), 2.32–2.24 (2H, m, Hax-4 + Heq-6), 1.99–1.92 (1H, m, Hax-6), 1.77 (3H, d, J=6.70 Hz, H3-7) δ(ax) 4.94 (1H, s, H-9), 4.65 (1H, s, H-9), 2.84–2.81 (1H, m, H-5), 2.69–2.63 (2H, m, H-3 + Heq-4) 2.58- 2.49 (2H, m, H-2 + Hax-4), 2.35–2.18 (2H, m, Heq + ax-6), 1.75 (3H, s, H-10); 1.25 (3H, d, J=6.70 Hz, H-7). 13C-NMR (CDCl3, δ): δ(eq) 206.73 (C-1), 145.55 (C-8), 118.65 (C-11), 111.16 (CH2-9), 45.79 (CH2-4), 45.05 (CH-2), 42.25 (CH-5), 35.67 (CH-3), 32.85 (CH2-6), 20.53 (CH3-10), 12.59 (CH3-7); δ(ax) 207.23 (C-1), 144.76 (C-8), 120.54 (C-11), 113.88 (CH2-9), 46.70 (CH2-4), 40.35 (CH-5), 31.96 (CH-3), 30.52 (CH2-6), 21.89 (CH3-10), 13.50 (CH3-7). IR– (CDCl3, ν(cm-1)): 2974, 2936, 2359, 2237, 1709, 1447, 1379, 898. MS (EI+) (m/z, %): 162.99 ([C11H14O]+, 4); 178.12 ([M+1]+, 57); 200.10 ([M+ Na]+, 100); 201.05 (12); 201.10 (16); 210 (10); 216 (5). HRMS: 177.2429 calculated for C11H15 NO and found 177.1145.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O0.1359 (3)0.16426 (13)0.97088 (8)0.0752 (4)
N0.1851 (4)0.20500 (17)0.92433 (12)0.0888 (6)
C10.5822 (3)0.06508 (16)0.94292 (9)0.0573 (4)
H10.71320.11430.96590.069*
C20.5121 (4)0.04653 (16)0.99035 (8)0.0588 (4)
H20.66890.09171.00020.071*
C30.3426 (3)0.13420 (15)0.95095 (9)0.0564 (4)
C40.4468 (4)0.17830 (18)0.88397 (11)0.0705 (5)
H4A0.59910.22660.89190.085*
H4B0.32430.23200.86170.085*
C50.5082 (4)0.06743 (17)0.83708 (9)0.0625 (4)
H50.35010.02220.82880.075*
C60.6881 (4)0.02143 (19)0.87410 (10)0.0646 (5)
H6A0.84840.02030.88160.078*
H6B0.71920.09350.84540.078*
C70.6110 (5)0.1083 (2)0.76790 (12)0.0885 (7)
C80.7980 (8)0.2010 (4)0.76281 (18)0.1574 (17)
H8A0.75140.25970.72800.236*
H8B0.95680.16310.75110.236*
H8C0.81370.24340.80580.236*
C90.5180 (13)0.0550 (7)0.71081 (16)0.263 (4)
H9A0.57760.07960.66810.316*
H9B0.39430.00630.71410.316*
C100.3602 (4)0.14556 (16)0.93301 (10)0.0642 (5)
C110.4019 (6)0.0058 (2)1.05820 (10)0.0901 (7)
H11A0.23790.03011.05090.135*
H11B0.38700.07681.08790.135*
H11C0.51110.05501.07890.135*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.0629 (8)0.0698 (8)0.0928 (10)0.0087 (7)0.0027 (7)0.0158 (7)
N0.1012 (14)0.0644 (10)0.1009 (14)0.0174 (11)0.0103 (12)0.0007 (9)
C10.0587 (9)0.0538 (8)0.0594 (9)0.0115 (7)0.0018 (7)0.0007 (7)
C20.0646 (10)0.0575 (8)0.0542 (8)0.0038 (8)0.0016 (8)0.0046 (7)
C30.0598 (9)0.0453 (7)0.0641 (9)0.0001 (7)0.0026 (8)0.0111 (6)
C40.0820 (13)0.0565 (9)0.0729 (11)0.0033 (9)0.0021 (10)0.0073 (8)
C50.0656 (10)0.0669 (10)0.0549 (9)0.0066 (9)0.0005 (8)0.0009 (8)
C60.0609 (10)0.0682 (10)0.0647 (9)0.0022 (9)0.0111 (8)0.0039 (8)
C70.1031 (17)0.0994 (15)0.0630 (11)0.0087 (15)0.0083 (12)0.0114 (11)
C80.179 (3)0.205 (4)0.0891 (19)0.075 (4)0.014 (2)0.044 (2)
C90.358 (9)0.365 (8)0.0663 (17)0.233 (8)0.047 (3)0.045 (3)
C100.0789 (12)0.0467 (8)0.0669 (10)0.0016 (9)0.0094 (9)0.0003 (7)
C110.129 (2)0.0840 (13)0.0578 (10)0.0202 (15)0.0180 (12)0.0017 (10)
Geometric parameters (Å, º) top
O—C31.205 (2)C5—C61.529 (3)
N—C101.137 (3)C5—H50.9800
C1—C101.470 (3)C6—H6A0.9700
C1—C61.531 (3)C6—H6B0.9700
C1—C21.559 (2)C7—C91.347 (5)
C1—H10.9800C7—C81.406 (5)
C2—C31.510 (2)C8—H8A0.9600
C2—C111.513 (3)C8—H8B0.9600
C2—H20.9800C8—H8C0.9600
C3—C41.498 (3)C9—H9A0.9300
C4—C51.536 (3)C9—H9B0.9300
C4—H4A0.9700C11—H11A0.9600
C4—H4B0.9700C11—H11B0.9600
C5—C71.522 (3)C11—H11C0.9600
C10—C1—C6110.83 (16)C4—C5—H5107.5
C10—C1—C2109.82 (15)C5—C6—C1112.29 (15)
C6—C1—C2112.06 (14)C5—C6—H6A109.1
C10—C1—H1108.0C1—C6—H6A109.1
C6—C1—H1108.0C5—C6—H6B109.1
C2—C1—H1108.0C1—C6—H6B109.1
C3—C2—C11113.48 (17)H6A—C6—H6B107.9
C3—C2—C1108.38 (13)C9—C7—C8119.8 (3)
C11—C2—C1113.08 (16)C9—C7—C5119.0 (3)
C3—C2—H2107.2C8—C7—C5121.2 (2)
C11—C2—H2107.2C7—C8—H8A109.5
C1—C2—H2107.2C7—C8—H8B109.5
O—C3—C4122.18 (18)H8A—C8—H8B109.5
O—C3—C2122.69 (18)C7—C8—H8C109.5
C4—C3—C2115.10 (16)H8A—C8—H8C109.5
C3—C4—C5110.84 (15)H8B—C8—H8C109.5
C3—C4—H4A109.5C7—C9—H9A120.0
C5—C4—H4A109.5C7—C9—H9B120.0
C3—C4—H4B109.5H9A—C9—H9B120.0
C5—C4—H4B109.5N—C10—C1178.0 (2)
H4A—C4—H4B108.1C2—C11—H11A109.5
C7—C5—C6112.20 (17)C2—C11—H11B109.5
C7—C5—C4112.55 (17)H11A—C11—H11B109.5
C6—C5—C4109.32 (15)C2—C11—H11C109.5
C7—C5—H5107.5H11A—C11—H11C109.5
C6—C5—H5107.5H11B—C11—H11C109.5
C10—C1—C2—C371.53 (18)C3—C4—C5—C655.5 (2)
C6—C1—C2—C352.1 (2)C7—C5—C6—C1178.64 (18)
C10—C1—C2—C1155.2 (2)C4—C5—C6—C155.8 (2)
C6—C1—C2—C11178.83 (19)C10—C1—C6—C567.67 (19)
C11—C2—C3—O2.8 (2)C2—C1—C6—C555.4 (2)
C1—C2—C3—O123.73 (18)C6—C5—C7—C9102.3 (5)
C11—C2—C3—C4179.06 (17)C4—C5—C7—C9133.9 (5)
C1—C2—C3—C454.45 (19)C6—C5—C7—C878.4 (3)
O—C3—C4—C5120.6 (2)C4—C5—C7—C845.4 (4)
C2—C3—C4—C557.6 (2)C6—C1—C10—N58 (6)
C3—C4—C5—C7179.12 (18)C2—C1—C10—N66 (6)
Acknowledgements top

This work was supported financially by the Xunta de Galicia (No. EXPTE. CN 2012/184). The work of the MS and X-ray divisions of the research support service of the University of Vigo (CACTI) is also gratefully acknowledged. MG thanks the University of Vigo for a PhD fellowship.

references
References top

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1995). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Wasserscheid, P. & Keim, W. (2000). Angew. Chem. Int. Ed. 39., 3772–3789.

Welton, T. (1999). Chem. Rev. 99, 2071–2084.