Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 5| May 2013| Page o799
https://doi.org/10.1107/S1600536813011197

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

Marcos L. Rivadulla,a Alioune Fall,a María Gonzáleza and Maria J. Matosb*

aDepartamento de Química Orgánica, Facultade de Química, Universidade de Vigo, E-36310 Vigo, Spain, and bDepartamento de Química Orgánica, Facultade de Farmacia, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
*Correspondence e-mail: mariacmatos@gmail.com

(Received 19 April 2013; accepted 24 April 2013; online 27 April 2013)

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.

Related literature

For recent review of Ionic liquids as solvents, see: Welton (1999[Welton, T. (1999). Chem. Rev. 99, 2071-2084.]); Wasserscheid & Keim (2000[Wasserscheid, P. & Keim, W. (2000). Angew. Chem. Int. Ed. 39., 3772-3789.]).

[Scheme 1]

Experimental

Crystal data

  • C11H15NO

  • Mr = 177.24

  • Orthorhombic, P 21 21 21

  • a = 5.2892 (8) Å

  • b = 10.7213 (16) Å

  • c = 19.559 (3) Å

  • V = 1109.1 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 293 K

  • 0.60 × 0.56 × 0.42 mm
Data collection

  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1995[Sheldrick, G. M. (1995). SADABS. University of Göttingen, Germany.]) Tmin = 0.861, Tmax = 1.000

  • 7138 measured reflections

  • 2590 independent reflections

  • 2112 reflections with I > 2σ(I)

  • Rint = 0.023
Refinement

  • R[F2 > 2σ(F2)] = 0.052

  • wR(F2) = 0.164

  • S = 1.04

  • 2590 reflections

  • 120 parameters

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813011197/go2087sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813011197/go2087Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813011197/go2087Isup3.cml

checkCIF report


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.

Structure description 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.

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

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 m−3
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 mm−1
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 = −6→6
Tmin = 0.861, Tmax = 1.000k = −13→13
7138 measured reflectionsl = −19→25
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 Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
C11H15NOV = 1109.1 (3) Å3
Mr = 177.24Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.2892 (8) ŵ = 0.07 mm−1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.164H-atom parameters constrained
S = 1.04Δρmax = 0.24 e Å−3
2590 reflectionsΔρmin = −0.20 e Å−3
120 parameters
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)
H10.7132−0.11430.96590.069*
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*
H6B0.7192−0.09350.84540.078*
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*
H9B0.3943−0.00630.71410.316*
C100.3602 (4)−0.14556 (16)0.93301 (10)0.0642 (5)
C110.4019 (6)0.0058 (2)1.05820 (10)0.0901 (7)
H11A0.2379−0.03011.05090.135*
H11B0.38700.07681.08790.135*
H11C0.5111−0.05501.07890.135*
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—C3−71.53 (18)C3—C4—C5—C6−55.5 (2)
C6—C1—C2—C352.1 (2)C7—C5—C6—C1−178.64 (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—O−2.8 (2)C2—C1—C6—C5−55.4 (2)
C1—C2—C3—O123.73 (18)C6—C5—C7—C9102.3 (5)
C11—C2—C3—C4179.06 (17)C4—C5—C7—C9−133.9 (5)
C1—C2—C3—C4−54.45 (19)C6—C5—C7—C8−78.4 (3)
O—C3—C4—C5−120.6 (2)C4—C5—C7—C845.4 (4)
C2—C3—C4—C557.6 (2)C6—C1—C10—N−58 (6)
C3—C4—C5—C7179.12 (18)C2—C1—C10—N66 (6)

Experimental details

Crystal data
Chemical formulaC11H15NO
Mr177.24
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)5.2892 (8), 10.7213 (16), 19.559 (3)
V (Å3)1109.1 (3)
Z4
Radiation typeMo Kα
µ (mm−1)0.07
Crystal size (mm)0.60 × 0.56 × 0.42
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1995)
Tmin, Tmax0.861, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		7138, 2590, 2112
Rint0.023
(sin θ/λ)max (Å−1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.164, 1.04
No. of reflections2590
No. of parameters120
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.24, −0.20
Absolute structure parameter−1 (2)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2007), PLATON (Spek, 2009).

 

Acknowledgements

This work was supported financially by the Xunta de Galicia (No. EXPTE. CN 2012/184). The work of the MS and Single-crystal X-ray Diffraction 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

First citationBruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationSheldrick, G. M. (1995). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWasserscheid, P. & Keim, W. (2000). Angew. Chem. Int. Ed. 39., 3772–3789.  CrossRef Google Scholar
 First citationWelton, T. (1999). Chem. Rev. 99, 2071–2084.  Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 5| May 2013| Page o799
https://doi.org/10.1107/S1600536813011197
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS