supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

wn2249 scheme

Acta Cryst. (2008). E64, o818    [ doi:10.1107/S1600536808009070 ]

1-Methyl-5-(4-methylphenyl)-3-oxocyclohexane-1-carbonitrile

R. T. S. Mohan, S. Kamatchi, M. Subramanyam, A. Thiruvalluvar and A. Linden

Abstract top

In the title molecule, C15H17NO, the cyclohexane ring adopts a chair conformation. The cyano and methyl groups at position 1 have axial and equatorial orientations, respectively. The benzene ring has an equatorial orientation. A C-H...[pi] interaction involving the benzene ring is found in the crystal structure.

Comment top

The title compound has been analysed as part of our crystallographic studies on substituted cyclohexanes (Subramanyam et al., 2007). Its molecular structure, with atomic numbering scheme, is shown in Fig. 1. The cyclohexane ring adopts a chair conformation. The cyano group and the methyl group at position 1 have axial and equatorial orientations respectively. The benzene ring at position 5 has an equatorial orientation. A C4—H4A···π(-x, y, 1/2 - z) interaction involving the benzene ring is found in the structure. No classical hydrogen bonds are found in the crystal structure.

Related literature top

Subramanyam et al. (2007) have reported the crystal structure of 3-cyano-3-methyl-5-phenylcyclohexane, in which the cyclohexane ring adopts a chair conformation.

Experimental top

A mixture of 5-4'-methylphenyl-3-methylcyclohex-2-enone (4.00 g, 0.02 mol), potassium cyanide (2.60 g, 0.04 mol), ammonium chloride (1.59 g, 0.03 mol), dimethylformamide (50 ml) and water (2 ml) was heated with stirring for 16-18 h at 353 K. The reaction mixture was cooled to room temperature and poured into water. The product was extracted with CH2Cl2 (3x10 ml) and the organic layer was dried, evaporated and purified by column chromatography (hexane-EtOAc, 4.5:1 v/v). The yield of the isolated product was 3.40 g (75%).

Refinement top

H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å for Csp2, 0.98 Å for methyl C, 0.99 Å for methylene C and 1.00 Å for methine C; Uiso(H) = xUeq(carrier atom), where x = 1.5 for methyl and 1.2 for all other C atoms

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are represented by spheres of arbitrary radius.
1-Methyl-5-(4-methylphenyl)-3-oxocyclohexane-1-carbonitrile top
Crystal data top
C15H17NOF000 = 976
Mr = 227.30Dx = 1.211 Mg m−3
Monoclinic, C2/cMelting point: 376 K
Hall symbol: -C 2ycMo Kα radiation
λ = 0.71073 Å
a = 23.4475 (5) ÅCell parameters from 3933 reflections
b = 6.0370 (1) Åθ = 2.0–30.0º
c = 21.0740 (5) ŵ = 0.08 mm−1
β = 123.267 (1)ºT = 160 (1) K
V = 2494.22 (9) Å3Tablet, colourless
Z = 80.25 × 0.20 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		3640 independent reflections
Radiation source: Nonius FR590 sealed tube generator2682 reflections with I > 2σ(I)
Monochromator: horizontally mounted graphite crystalRint = 0.054
Detector resolution: 9 pixels mm-1θmax = 30.1º
T = 160(1) Kθmin = 2.1º
φ and ω scans with κ offsetsh = 0→32
Absorption correction: nonek = 0→8
37687 measured reflectionsl = −29→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.170  w = 1/[σ2(Fo2) + (0.0889P)2 + 1.0674P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3640 reflectionsΔρmax = 0.42 e Å−3
154 parametersΔρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C15H17NOV = 2494.22 (9) Å3
Mr = 227.30Z = 8
Monoclinic, C2/cMo Kα
a = 23.4475 (5) ŵ = 0.08 mm−1
b = 6.0370 (1) ÅT = 160 (1) K
c = 21.0740 (5) Å0.25 × 0.20 × 0.10 mm
β = 123.267 (1)º
Data collection top
Nonius KappaCCD area-detector
diffractometer		3640 independent reflections
Absorption correction: none2682 reflections with I > 2σ(I)
37687 measured reflectionsRint = 0.054
Refinement top
R[F2 > 2σ(F2)] = 0.052154 parameters
wR(F2) = 0.170H-atom parameters constrained
S = 1.08Δρmax = 0.42 e Å−3
3640 reflectionsΔρmin = −0.27 e Å−3
Special details top

Experimental. Solvent used: ? Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.608 (1) Frames collected: 469 Seconds exposure per frame: 68 Degrees rotation per frame: 1.7 Crystal-Detector distance (mm): 30.0

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O3−0.15528 (6)0.46344 (19)0.25177 (7)0.0415 (4)
N12−0.08326 (7)0.6151 (2)0.47679 (8)0.0396 (4)
C1−0.11894 (7)0.9214 (2)0.37288 (8)0.0257 (4)
C2−0.16638 (7)0.8175 (3)0.29352 (8)0.0301 (4)
C3−0.13059 (7)0.6453 (2)0.27576 (7)0.0284 (4)
C4−0.06263 (7)0.7130 (2)0.28980 (8)0.0285 (4)
C5−0.01555 (6)0.8211 (2)0.36851 (7)0.0235 (3)
C6−0.05364 (7)1.0065 (2)0.37989 (8)0.0257 (4)
C11−0.15578 (8)1.1085 (3)0.38596 (10)0.0358 (5)
C12−0.09953 (7)0.7479 (2)0.43103 (8)0.0283 (4)
C150.24199 (7)1.0891 (3)0.40745 (9)0.0366 (5)
C510.05077 (6)0.8959 (2)0.37806 (7)0.0234 (3)
C520.10525 (7)0.7488 (2)0.40770 (7)0.0268 (4)
C530.16606 (7)0.8088 (2)0.41545 (8)0.0288 (4)
C540.17508 (7)1.0191 (3)0.39554 (8)0.0283 (4)
C550.12020 (7)1.1653 (2)0.36508 (9)0.0321 (4)
C560.05907 (7)1.1049 (2)0.35635 (9)0.0308 (4)
H2A−0.205920.748440.290890.0361*
H2B−0.183880.935830.254690.0361*
H4A−0.070290.818890.249980.0341*
H4B−0.039700.580690.286000.0341*
H5−0.003870.705020.407710.0282*
H6A−0.065991.123600.341550.0308*
H6B−0.023131.073050.430720.0308*
H11A−0.168731.224890.347970.0537*
H11B−0.125311.170520.436860.0537*
H11C−0.196801.049420.381410.0537*
H15A0.274350.965500.429150.0549*
H15B0.260391.215510.442280.0549*
H15C0.234751.131600.358660.0549*
H520.100860.605080.422900.0321*
H530.202090.703960.434700.0345*
H550.124641.309170.349970.0384*
H560.022421.207750.335260.0370*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0412 (6)0.0397 (6)0.0472 (7)−0.0142 (5)0.0266 (5)−0.0148 (5)
N120.0409 (7)0.0425 (8)0.0396 (7)−0.0060 (6)0.0248 (6)0.0051 (6)
C10.0254 (6)0.0250 (6)0.0306 (7)−0.0027 (5)0.0178 (6)−0.0022 (5)
C20.0233 (6)0.0366 (8)0.0285 (7)−0.0015 (6)0.0130 (5)−0.0014 (6)
C30.0273 (7)0.0332 (8)0.0231 (7)−0.0052 (5)0.0129 (5)−0.0028 (5)
C40.0283 (7)0.0303 (7)0.0304 (7)−0.0032 (5)0.0184 (6)−0.0045 (5)
C50.0224 (6)0.0230 (6)0.0265 (6)−0.0008 (5)0.0144 (5)0.0021 (5)
C60.0258 (6)0.0246 (7)0.0301 (7)−0.0042 (5)0.0176 (6)−0.0030 (5)
C110.0364 (8)0.0305 (8)0.0515 (9)−0.0015 (6)0.0311 (7)−0.0045 (7)
C120.0258 (6)0.0329 (7)0.0303 (7)−0.0071 (5)0.0181 (6)−0.0048 (6)
C150.0275 (7)0.0443 (9)0.0427 (9)−0.0070 (6)0.0222 (7)−0.0033 (7)
C510.0229 (6)0.0248 (6)0.0241 (6)−0.0018 (5)0.0140 (5)0.0003 (5)
C520.0258 (6)0.0264 (7)0.0272 (7)−0.0003 (5)0.0140 (5)0.0040 (5)
C530.0232 (6)0.0332 (7)0.0281 (7)0.0030 (5)0.0128 (5)0.0034 (6)
C540.0249 (6)0.0340 (7)0.0289 (7)−0.0052 (5)0.0167 (6)−0.0035 (5)
C550.0346 (7)0.0252 (7)0.0450 (9)−0.0036 (6)0.0273 (7)0.0009 (6)
C560.0296 (7)0.0258 (7)0.0428 (8)0.0033 (5)0.0235 (7)0.0056 (6)
Geometric parameters (Å, °) top
O3—C31.2145 (17)C2—H2A0.9900
N12—C121.1466 (19)C2—H2B0.9900
C1—C21.545 (2)C4—H4A0.9900
C1—C61.543 (3)C4—H4B0.9900
C1—C111.536 (3)C5—H51.0000
C1—C121.4812 (19)C6—H6A0.9900
C2—C31.507 (2)C6—H6B0.9900
C3—C41.509 (3)C11—H11A0.9800
C4—C51.5450 (19)C11—H11B0.9800
C5—C61.531 (2)C11—H11C0.9800
C5—C511.523 (2)C15—H15A0.9800
C15—C541.507 (3)C15—H15B0.9800
C51—C521.391 (2)C15—H15C0.9800
C51—C561.3917 (18)C52—H520.9500
C52—C531.391 (3)C53—H530.9500
C53—C541.389 (2)C55—H550.9500
C54—C551.393 (2)C56—H560.9500
C55—C561.390 (3)
O3···H6Ai2.8000H4A···C55vii2.9200
O3···H11Ai2.6400H4A···C56vii2.9500
O3···H15Cii2.8500H4B···C523.1000
O3···H55ii2.7700H4B···H56i2.5700
N12···H11Bi2.8200H5···C122.5600
N12···H5iii2.8900H5···H522.3700
N12···H6Biv2.8700H5···N12iii2.8900
N12···H52iii2.7100H6A···O3ix2.8000
C4···C123.532 (2)H6A···C562.7800
C12···C43.532 (2)H6A···H2B2.5900
C12···C15v3.598 (3)H6A···H11A2.5600
C15···C12vi3.598 (3)H6A···H562.2100
C6···H562.7200H6B···C563.0900
C12···H52.5600H6B···H11B2.5400
C12···H6Biv2.9600H6B···N12iv2.8700
C15···H2Bvii3.0500H6B···C12iv2.9600
C51···H4Avii3.0100H11A···O3ix2.6400
C52···H4B3.1000H11A···H2B2.5000
C52···H55i3.0600H11A···H6A2.5600
C52···H4Avii2.9800H11B···N12ix2.8200
C52···H11Biv3.0800H11B···H6B2.5400
C53···H4Avii2.9300H11B···C52iv3.0800
C53···H53viii2.9700H11C···H2A2.5600
C54···H4Avii2.9400H15A···H532.3700
C55···H52ix3.0600H15C···O3x2.8500
C55···H4Avii2.9200H15C···H2Bvii2.3200
C56···H6A2.7800H15C···H2Avi2.5800
C56···H6B3.0900H52···C55i3.0600
C56···H4Avii2.9500H52···H52.3700
H2A···H11C2.5600H52···N12iii2.7100
H2A···H15Cv2.5800H53···H15A2.3700
H2B···H6A2.5900H53···C53viii2.9700
H2B···H11A2.5000H53···H53viii2.4800
H2B···C15vii3.0500H55···C52ix3.0600
H2B···H15Cvii2.3200H55···O3x2.7700
H4A···C51vii3.0100H56···C62.7200
H4A···C52vii2.9800H56···H4Bix2.5700
H4A···C53vii2.9300H56···H6A2.2100
H4A···C54vii2.9400
C2—C1—C6109.04 (13)C3—C4—H4B109.00
C2—C1—C11110.55 (14)C5—C4—H4A109.00
C2—C1—C12108.69 (11)C5—C4—H4B109.00
C6—C1—C11111.35 (12)H4A—C4—H4B108.00
C6—C1—C12108.53 (13)C4—C5—H5108.00
C11—C1—C12108.62 (14)C6—C5—H5108.00
C1—C2—C3112.38 (13)C51—C5—H5108.00
O3—C3—C2121.60 (17)C1—C6—H6A109.00
O3—C3—C4122.51 (15)C1—C6—H6B109.00
C2—C3—C4115.89 (12)C5—C6—H6A109.00
C3—C4—C5112.38 (13)C5—C6—H6B109.00
C4—C5—C6110.02 (12)H6A—C6—H6B108.00
C4—C5—C51110.09 (12)C1—C11—H11A109.00
C6—C5—C51113.81 (11)C1—C11—H11B109.00
C1—C6—C5112.03 (11)C1—C11—H11C109.00
N12—C12—C1178.70 (18)H11A—C11—H11B109.00
C5—C51—C52119.32 (12)H11A—C11—H11C109.00
C5—C51—C56122.83 (13)H11B—C11—H11C109.00
C52—C51—C56117.83 (15)C54—C15—H15A109.00
C51—C52—C53121.07 (12)C54—C15—H15B109.00
C52—C53—C54121.23 (14)C54—C15—H15C109.00
C15—C54—C53121.54 (16)H15A—C15—H15B109.00
C15—C54—C55120.88 (16)H15A—C15—H15C109.00
C53—C54—C55117.58 (17)H15B—C15—H15C109.00
C54—C55—C56121.31 (13)C51—C52—H52119.00
C51—C56—C55120.95 (14)C53—C52—H52119.00
C1—C2—H2A109.00C52—C53—H53119.00
C1—C2—H2B109.00C54—C53—H53119.00
C3—C2—H2A109.00C54—C55—H55119.00
C3—C2—H2B109.00C56—C55—H55119.00
H2A—C2—H2B108.00C51—C56—H56120.00
C3—C4—H4A109.00C55—C56—H56120.00
C6—C1—C2—C352.74 (16)C4—C5—C51—C52−88.85 (14)
C11—C1—C2—C3175.47 (14)C4—C5—C51—C5689.28 (15)
C12—C1—C2—C3−65.40 (19)C6—C5—C51—C52147.10 (12)
C2—C1—C6—C5−58.85 (15)C6—C5—C51—C56−34.77 (17)
C11—C1—C6—C5178.91 (12)C5—C51—C52—C53178.29 (12)
C12—C1—C6—C559.39 (14)C56—C51—C52—C530.1 (2)
C1—C2—C3—O3130.73 (15)C5—C51—C56—C55−179.06 (13)
C1—C2—C3—C4−49.13 (17)C52—C51—C56—C55−0.9 (2)
O3—C3—C4—C5−131.91 (13)C51—C52—C53—C541.5 (2)
C2—C3—C4—C547.96 (15)C52—C53—C54—C15176.87 (13)
C3—C4—C5—C6−51.08 (14)C52—C53—C54—C55−2.2 (2)
C3—C4—C5—C51−177.30 (10)C15—C54—C55—C56−177.71 (14)
C4—C5—C6—C158.21 (15)C53—C54—C55—C561.3 (2)
C51—C5—C6—C1−177.70 (11)C54—C55—C56—C510.2 (2)
Symmetry codes: (i) x, y−1, z; (ii) −x, y−1, −z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1; (v) x−1/2, y−1/2, z; (vi) x+1/2, y+1/2, z; (vii) −x, y, −z+1/2; (viii) −x+1/2, −y+3/2, −z+1; (ix) x, y+1, z; (x) −x, y+1, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···Cgvii0.992.613.5425 (15)157
Symmetry codes: (vii) −x, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···Cgi0.992.613.5425 (15)157
Symmetry codes: (i) −x, y, −z+1/2.
Acknowledgements top

AT thanks the UGC, India, for the award of a Minor Research Project [File No. MRP-2355/06(UGC-SERO), Link No. 2355, 10/01/2007].

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C.W. Carter & R.M. Sweet, pp. 307–326. London: Academic Press.

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

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Subramanyam, M., Thiruvalluvar, A., Sabapathy Mohan, R. T. & Kamatchi, S. (2007). Acta Cryst. E63, o2715–o2716.