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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3065.
Published online 2009 November 11. doi:  10.1107/S1600536809047175
PMCID: PMC2972109

2-(7-Methyl-3-oxo-1-phenyl­perhydro­naphthalen-4a-yl)malononitrile

Abstract

In the title compound, C20H22N2O, both cyclo­hexane rings adopt chair conformations. Weak C—H(...)N and C—H(...)O hydrogen bonding is present in the crystal structure.

Related literature

For the use of malononitrile-containing compounds as building blocks in organic synthesis, see: Magdi et al. (2003 [triangle]); Michail & Sergey (2008 [triangle]); Zhang et al. (2008 [triangle]). For a related structure, see: Zhou et al. (2007 [triangle]).

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Object name is e-65-o3065-scheme1.jpg

Experimental

Crystal data

  • C20H22N2O
  • M r = 306.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3065-efi1.jpg
  • a = 11.575 (2) Å
  • b = 6.0907 (12) Å
  • c = 12.276 (3) Å
  • β = 101.38 (3)°
  • V = 848.4 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 113 K
  • 0.25 × 0.24 × 0.21 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: none
  • 7044 measured reflections
  • 2194 independent reflections
  • 1479 reflections with I > 2σ(I)
  • R int = 0.063

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.083
  • S = 1.04
  • 2194 reflections
  • 209 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047175/xu2670sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047175/xu2670Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The diffraction data were collected at the Centre for Testing and Analysis, Sichuan University. We acknowledge financial support from China West Normal University (No 412374).

supplementary crystallographic information

Comment

Malononitrile derivatives are useful intermediates in organic synthesis (Michail et al. 2008; Zhang et al. 2008; Zhou et al. 2007). Their potential applications are used for the preparation of heterocyclic ring compounds (Magdi et al. 2003). As a part of our interest in the synthsis of some complex ring systems, we investigated the title compound, (I), which is a potential precursor in the preparation of multifunctional tricyclic compound. We report herein the crystal structure of the title compound.

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. Two six membered rings (cyclohexanone and cyclohexane) adopt an chair conformation. The crystal packing is stabilized by C—H···N and C—H···0 hydrogen bonding (Table 1).

Experimental

2-(4-methylcyclohexylidene)malononitrile (0.16 g, 1 mmol), (E)-4-phenylbut-3-en-2-one (0.175 g, 1.2 mmol), 9S-amino-9-deoxyepiquinine (0.065 g, 0.2 mmol), 2,2,2-trifluoroacetic acid (0.029 g, 0.4 mmol) and N-ethyl-N-isopropylpropan-2-amine (0.023 g, 0.15 mmol) were stirred in THF (3 ml) at 298 K for 110 h. Then the reaction was quenched by adding 1 mol/L HCl (5 ml). The mixture was extracted with ethyl acetate (20 ml), dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure and flash chromatography on silica gel gave the pure compound as a white solid. Colorless single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation the mixture solvents of ethyl acetate and petroleum ether.

Refinement

The carbon-bound hydrogen atoms were placed in calculated positions, with C—H = 0.95–1.00 Å, and refined using a riding model, with Uiso(H) =1.5Ueq(C) for methyl H atom and 1.2Ueq(C) for the others. In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

Figures

Fig. 1.
The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

Crystal data

C20H22N2OF(000) = 328
Mr = 306.40Dx = 1.199 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2724 reflections
a = 11.575 (2) Åθ = 3.4–27.9°
b = 6.0907 (12) ŵ = 0.07 mm1
c = 12.276 (3) ÅT = 113 K
β = 101.38 (3)°Block, colourless
V = 848.4 (3) Å30.25 × 0.24 × 0.21 mm
Z = 2

Data collection

Rigaku Saturn CCD area-detector diffractometer1479 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.063
confocalθmax = 27.9°, θmin = 3.4°
Detector resolution: 7.31 pixels mm-1h = −15→15
ω and [var phi] scansk = −7→7
7044 measured reflectionsl = −14→16
2194 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.021P)2] where P = (Fo2 + 2Fc2)/3
2194 reflections(Δ/σ)max < 0.001
209 parametersΔρmax = 0.22 e Å3
1 restraintΔρmin = −0.24 e Å3

Special details

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)

xyzUiso*/Ueq
O10.59916 (14)0.6258 (3)0.05489 (13)0.0319 (4)
N10.3799 (2)0.3869 (4)0.41898 (18)0.0389 (6)
N20.40092 (18)−0.1712 (4)0.21854 (19)0.0354 (6)
C10.61036 (19)0.2632 (4)0.27728 (18)0.0183 (5)
C20.71015 (19)0.1075 (4)0.25731 (17)0.0193 (5)
H20.6728−0.02670.21850.023*
C30.7857 (2)0.2188 (4)0.18092 (18)0.0204 (5)
H30.81980.35560.21940.025*
C40.8884 (2)0.0760 (4)0.16412 (18)0.0223 (6)
C51.0035 (2)0.1440 (4)0.20656 (19)0.0272 (6)
H51.01690.28120.24370.033*
C61.0987 (2)0.0139 (5)0.1952 (2)0.0330 (7)
H61.17660.06340.22390.040*
C71.0812 (2)−0.1863 (5)0.1427 (2)0.0329 (7)
H71.1466−0.27650.13670.040*
C80.9677 (2)−0.2551 (4)0.0988 (2)0.0330 (6)
H80.9550−0.39190.06120.040*
C90.8720 (2)−0.1242 (4)0.10967 (19)0.0283 (6)
H90.7943−0.17290.07930.034*
C100.7070 (2)0.2892 (4)0.07005 (18)0.0261 (6)
H10A0.75550.36440.02340.031*
H10B0.67110.15780.02940.031*
C110.6119 (2)0.4407 (4)0.09118 (19)0.0239 (6)
C120.5360 (2)0.3476 (4)0.16652 (17)0.0220 (5)
H12A0.48840.22510.12810.026*
H12B0.48110.46250.18240.026*
C130.7868 (2)0.0355 (4)0.36900 (18)0.0207 (5)
H13A0.7386−0.05620.40940.025*
H13B0.8525−0.05630.35400.025*
C140.8377 (2)0.2275 (4)0.44301 (19)0.0233 (6)
H140.89210.31000.40390.028*
C150.7405 (2)0.3855 (4)0.46116 (18)0.0226 (5)
H15A0.77680.51700.50130.027*
H15B0.69120.31320.50800.027*
C160.6622 (2)0.4565 (4)0.35109 (18)0.0207 (5)
H16A0.70930.54880.30970.025*
H16B0.59690.54770.36730.025*
C170.9091 (2)0.1482 (5)0.55366 (19)0.0341 (7)
H17A0.85800.06400.59320.051*
H17B0.94140.27500.59870.051*
H17C0.97370.05460.54030.051*
C180.52557 (19)0.1314 (4)0.33947 (18)0.0213 (5)
H180.57550.05680.40480.026*
C190.4415 (2)0.2767 (4)0.38201 (19)0.0255 (6)
C200.4563 (2)−0.0388 (4)0.2708 (2)0.0235 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0308 (10)0.0322 (11)0.0298 (9)0.0017 (9)−0.0009 (8)0.0110 (9)
N10.0373 (14)0.0422 (15)0.0404 (13)−0.0023 (12)0.0155 (11)−0.0142 (12)
N20.0259 (12)0.0288 (14)0.0513 (14)−0.0010 (11)0.0073 (11)−0.0060 (12)
C10.0163 (12)0.0199 (13)0.0181 (11)0.0011 (10)0.0022 (9)0.0019 (10)
C20.0195 (12)0.0195 (13)0.0180 (11)−0.0005 (11)0.0010 (9)−0.0021 (11)
C30.0183 (12)0.0233 (14)0.0196 (11)0.0020 (11)0.0035 (10)0.0007 (11)
C40.0211 (13)0.0274 (16)0.0196 (12)−0.0006 (12)0.0070 (10)0.0021 (11)
C50.0239 (13)0.0336 (15)0.0247 (12)−0.0001 (13)0.0063 (10)0.0019 (12)
C60.0208 (14)0.0470 (19)0.0315 (14)0.0015 (13)0.0059 (11)0.0048 (13)
C70.0273 (15)0.0419 (19)0.0326 (14)0.0129 (14)0.0133 (12)0.0085 (13)
C80.0396 (17)0.0318 (15)0.0309 (14)0.0053 (14)0.0150 (13)−0.0003 (13)
C90.0258 (14)0.0293 (15)0.0309 (14)0.0007 (12)0.0086 (11)−0.0004 (12)
C100.0274 (14)0.0332 (15)0.0192 (12)0.0010 (12)0.0080 (10)0.0044 (11)
C110.0213 (13)0.0314 (16)0.0164 (11)0.0014 (12)−0.0030 (10)0.0017 (11)
C120.0190 (12)0.0245 (14)0.0200 (12)0.0018 (12)−0.0019 (10)−0.0005 (11)
C130.0181 (12)0.0232 (14)0.0204 (12)0.0028 (11)0.0030 (10)0.0020 (10)
C140.0193 (12)0.0283 (14)0.0211 (12)0.0004 (11)0.0012 (10)0.0020 (11)
C150.0204 (13)0.0235 (14)0.0224 (12)0.0002 (11)0.0001 (10)−0.0021 (11)
C160.0190 (12)0.0195 (13)0.0232 (12)0.0018 (11)0.0032 (10)−0.0012 (11)
C170.0278 (14)0.0434 (17)0.0275 (13)0.0072 (14)−0.0036 (11)−0.0005 (13)
C180.0178 (11)0.0218 (12)0.0239 (12)0.0023 (11)0.0031 (10)0.0000 (11)
C190.0228 (13)0.0311 (15)0.0237 (12)−0.0063 (13)0.0070 (11)−0.0056 (12)
C200.0192 (13)0.0230 (14)0.0295 (14)0.0035 (12)0.0081 (11)0.0008 (12)

Geometric parameters (Å, °)

O1—C111.211 (3)C10—C111.498 (3)
N1—C191.137 (3)C10—H10A0.9900
N2—C201.145 (3)C10—H10B0.9900
C1—C161.534 (3)C11—C121.506 (3)
C1—C121.547 (3)C12—H12A0.9900
C1—C21.551 (3)C12—H12B0.9900
C1—C181.577 (3)C13—C141.526 (3)
C2—C131.543 (3)C13—H13A0.9900
C2—C31.558 (3)C13—H13B0.9900
C2—H21.0000C14—C171.522 (3)
C3—C41.520 (3)C14—C151.530 (3)
C3—C101.542 (3)C14—H141.0000
C3—H31.0000C15—C161.533 (3)
C4—C91.386 (3)C15—H15A0.9900
C4—C51.395 (3)C15—H15B0.9900
C5—C61.386 (3)C16—H16A0.9900
C5—H50.9500C16—H16B0.9900
C6—C71.375 (4)C17—H17A0.9800
C6—H60.9500C17—H17B0.9800
C7—C81.384 (4)C17—H17C0.9800
C7—H70.9500C18—C201.470 (3)
C8—C91.392 (3)C18—C191.484 (3)
C8—H80.9500C18—H181.0000
C9—H90.9500
C16—C1—C12110.45 (19)C11—C12—C1111.99 (18)
C16—C1—C2110.22 (18)C11—C12—H12A109.2
C12—C1—C2111.52 (17)C1—C12—H12A109.2
C16—C1—C18108.26 (17)C11—C12—H12B109.2
C12—C1—C18107.66 (17)C1—C12—H12B109.2
C2—C1—C18108.61 (18)H12A—C12—H12B107.9
C13—C2—C1110.43 (16)C14—C13—C2113.48 (19)
C13—C2—C3111.48 (18)C14—C13—H13A108.9
C1—C2—C3110.66 (18)C2—C13—H13A108.9
C13—C2—H2108.1C14—C13—H13B108.9
C1—C2—H2108.1C2—C13—H13B108.9
C3—C2—H2108.1H13A—C13—H13B107.7
C4—C3—C10112.40 (17)C17—C14—C13111.5 (2)
C4—C3—C2112.31 (18)C17—C14—C15110.78 (19)
C10—C3—C2110.42 (18)C13—C14—C15111.13 (19)
C4—C3—H3107.1C17—C14—H14107.8
C10—C3—H3107.1C13—C14—H14107.8
C2—C3—H3107.1C15—C14—H14107.8
C9—C4—C5118.1 (2)C14—C15—C16111.88 (18)
C9—C4—C3122.2 (2)C14—C15—H15A109.2
C5—C4—C3119.7 (2)C16—C15—H15A109.2
C6—C5—C4120.8 (2)C14—C15—H15B109.2
C6—C5—H5119.6C16—C15—H15B109.2
C4—C5—H5119.6H15A—C15—H15B107.9
C7—C6—C5120.5 (2)C15—C16—C1113.49 (18)
C7—C6—H6119.7C15—C16—H16A108.9
C5—C6—H6119.7C1—C16—H16A108.9
C6—C7—C8119.4 (2)C15—C16—H16B108.9
C6—C7—H7120.3C1—C16—H16B108.9
C8—C7—H7120.3H16A—C16—H16B107.7
C7—C8—C9120.1 (3)C14—C17—H17A109.5
C7—C8—H8119.9C14—C17—H17B109.5
C9—C8—H8119.9H17A—C17—H17B109.5
C4—C9—C8120.9 (2)C14—C17—H17C109.5
C4—C9—H9119.5H17A—C17—H17C109.5
C8—C9—H9119.5H17B—C17—H17C109.5
C11—C10—C3110.17 (18)C20—C18—C19107.53 (19)
C11—C10—H10A109.6C20—C18—C1113.71 (18)
C3—C10—H10A109.6C19—C18—C1112.4 (2)
C11—C10—H10B109.6C20—C18—H18107.7
C3—C10—H10B109.6C19—C18—H18107.7
H10A—C10—H10B108.1C1—C18—H18107.7
O1—C11—C10123.4 (2)N1—C19—C18177.1 (3)
O1—C11—C12122.2 (2)N2—C20—C18178.7 (2)
C10—C11—C12114.3 (2)
C16—C1—C2—C1354.0 (2)C3—C10—C11—O1120.9 (2)
C12—C1—C2—C13177.03 (19)C3—C10—C11—C12−56.3 (3)
C18—C1—C2—C13−64.5 (2)O1—C11—C12—C1−124.1 (2)
C16—C1—C2—C3−69.9 (2)C10—C11—C12—C153.1 (3)
C12—C1—C2—C353.1 (2)C16—C1—C12—C1172.3 (2)
C18—C1—C2—C3171.61 (17)C2—C1—C12—C11−50.7 (3)
C13—C2—C3—C453.7 (2)C18—C1—C12—C11−169.7 (2)
C1—C2—C3—C4177.04 (18)C1—C2—C13—C14−55.3 (2)
C13—C2—C3—C10−179.95 (19)C3—C2—C13—C1468.2 (2)
C1—C2—C3—C10−56.6 (2)C2—C13—C14—C17178.06 (19)
C10—C3—C4—C9−60.6 (3)C2—C13—C14—C1553.9 (2)
C2—C3—C4—C964.7 (3)C17—C14—C15—C16−176.4 (2)
C10—C3—C4—C5120.9 (2)C13—C14—C15—C16−51.9 (3)
C2—C3—C4—C5−113.8 (2)C14—C15—C16—C153.7 (3)
C9—C4—C5—C6−0.5 (3)C12—C1—C16—C15−178.17 (18)
C3—C4—C5—C6178.1 (2)C2—C1—C16—C15−54.5 (2)
C4—C5—C6—C7−0.7 (4)C18—C1—C16—C1564.2 (2)
C5—C6—C7—C81.5 (4)C16—C1—C18—C20171.35 (19)
C6—C7—C8—C9−1.2 (4)C12—C1—C18—C2051.9 (2)
C5—C4—C9—C80.8 (3)C2—C1—C18—C20−69.0 (2)
C3—C4—C9—C8−177.8 (2)C16—C1—C18—C1948.9 (2)
C7—C8—C9—C40.1 (4)C12—C1—C18—C19−70.5 (2)
C4—C3—C10—C11−176.4 (2)C2—C1—C18—C19168.59 (18)
C2—C3—C10—C1157.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.952.543.451 (3)162
C12—H12A···O1ii0.992.353.159 (2)138
C18—H18···N1iii1.002.363.306 (3)157

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z; (iii) −x+1, y−1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2670).

References

  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Magdi, E. A., Zaki, M., Fernanda, P. & Brian, L. B. (2003). J. Org. Chem. 68, 276–282. [PubMed]
  • Michail, N. E. & Sergey, K. F. (2008). Tetrahedron, 64, 708–713.
  • Rigaku/MSC (2005). CrystalClear and CrystalStructure, Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, D.-J., Wang, G.-X. & Zhu, R.-X. (2008). Tetrahedron Asymmetry, 19, 568–576.
  • Zhou, J.-X., Wang, X.-S. & Shi, D.-Q. (2007). Acta Cryst. E63, o2082–o2083.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography