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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1346.
Published online 2009 May 20. doi:  10.1107/S1600536809018479
PMCID: PMC2969624

4,4-Dimethyl-1-(3-nitro­phen­yl)pent-1-en-3-one

Abstract

All the non-hydrogen atoms except one methyl C atom of the title compound, C13H15NO3, lie on a crystallographic mirror plane perpendicular to the b axis. The crystal packing is stabilized by two weak inter­molecular C—H(...)O hydrogen bonds.

Related literature

The title compound is an important intermediate in the pesticides industry (Wang et al., 2006 [triangle]). For related structures, see: Anuradha et al. (2008 [triangle]); Butcher et al. (2007 [triangle]); Gong et al. (2008 [triangle]); Harrison et al. (2007 [triangle]); Patil et al. (2007 [triangle]); Sarojini et al. (2007 [triangle]); Thiruvalluvar et al. (2007 [triangle], 2008 [triangle]); Xia & Hu (2008 [triangle]).

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Object name is e-65-o1346-scheme1.jpg

Experimental

Crystal data

  • C13H15NO3
  • M r = 233.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1346-efi1.jpg
  • a = 11.3375 (9) Å
  • b = 7.2163 (6) Å
  • c = 14.9327 (12) Å
  • V = 1221.72 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 173 K
  • 0.48 × 0.36 × 0.15 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.958, T max = 0.987
  • 5485 measured reflections
  • 1280 independent reflections
  • 937 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.123
  • S = 1.06
  • 1280 reflections
  • 101 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018479/bt2958sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018479/bt2958Isup2.hkl

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

Acknowledgments

The authors express their thanks to the National Key Technology R&D Program (No. 2006BAE01A01-4).

supplementary crystallographic information

Comment

The title compound, 1-(3-nitrophenyl)-4,4-dimethylpentan-3-one, is a very important intermediate in the pesticides industry (Wang et al., 2006). Continuing our work (Xia & Hu, 2008), we report the synthesis and crystal structure of the title compound. Several crystal structures containing phenylprop-2-en-1-one moiety have been recently published (Anuradha et al., 2008; Butcher et al., 2007; Gong et al., 2008; Harrison et al., 2007; Patil et al., 2007; Sarojini et al., 2007; Thiruvalluvar et al., 2007, 2008; Xia & Hu, 2008). In the title compound (Fig. 1), the carbonyl, ethenyl and nitro groups are coplanar with the benzene ring. The bond lengths and bond angles in (I) are in excellent agreement with the corresponding bond lengths and angles reported in the related compounds given above. The crystal packing is illustrated in Fig. 2.

Experimental

3,3-dimethylbutan-2-one(0.0105 mol) was added dropwise into the solution of 3-nitrobenzaldehyde (0.01 mol) and 60 ml ethanol. Then 0.1 g 50% NaOH solution as catalyzer was added and the solution was stirred at 333 K for 5 h (monitored by TLC). Part of the solvent was evaporated and the solution was cooled to 277 K and a precipitate formed. It was filtered and dried. Crystals suitable for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

H atoms were positioned geometrically (C—H = 0.95 or Cmethyl-H = 0.98 Å) with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The methyl group on a general position was allowed to rotate but not to tip.

Figures

Fig. 1.
Molecular structure of the title compound, showing 30% probability displacement ellipsoids.
Fig. 2.
Packing diagram of the title compound.

Crystal data

C13H15NO3Dx = 1.268 Mg m3
Mr = 233.26Melting point: 363 K
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 1920 reflections
a = 11.3375 (9) Åθ = 2.3–27.7°
b = 7.2163 (6) ŵ = 0.09 mm1
c = 14.9327 (12) ÅT = 173 K
V = 1221.72 (17) Å3Block, colourless
Z = 40.48 × 0.36 × 0.15 mm
F(000) = 496

Data collection

Bruker SMART 1000 CCD diffractometer1280 independent reflections
Radiation source: fine-focus sealed tube937 reflections with I > 2σ(I)
graphiteRint = 0.030
ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)h = −13→12
Tmin = 0.958, Tmax = 0.987k = −3→8
5485 measured reflectionsl = −18→17

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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0591P)2 + 0.3634P] where P = (Fo2 + 2Fc2)/3
1280 reflections(Δ/σ)max = 0.001
101 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.16 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*/UeqOcc. (<1)
C10.64133 (19)0.25000.12364 (15)0.0363 (6)
H10.72490.25000.12810.044*
C20.5825 (2)0.25000.19956 (15)0.0371 (6)
H20.49870.25000.19830.045*
C30.6446 (2)0.25000.28774 (15)0.0367 (6)
C40.56797 (18)0.25000.37208 (15)0.0317 (5)
C50.6474 (2)0.25000.45437 (16)0.0392 (6)
H5A0.59870.25000.50860.059*
H5B0.69730.36090.45370.059*0.50
H5C0.69730.13910.45370.059*0.50
C60.48919 (15)0.0777 (3)0.37212 (12)0.0419 (5)
H6A0.5385−0.03380.37010.063*
H6B0.43740.08030.31960.063*
H6C0.44120.07610.42670.063*
C70.59173 (19)0.25000.03248 (15)0.0310 (5)
C80.66910 (19)0.2500−0.03967 (15)0.0313 (5)
H80.75190.2500−0.02990.038*
C90.62418 (18)0.2500−0.12592 (14)0.0296 (5)
C100.5051 (2)0.2500−0.14355 (15)0.0348 (6)
H100.47640.2500−0.20330.042*
C110.42813 (19)0.2500−0.07129 (16)0.0381 (6)
H110.34540.2500−0.08140.046*
C120.47098 (19)0.25000.01538 (15)0.0363 (6)
H120.41710.25000.06410.044*
N10.70773 (17)0.2500−0.20150 (12)0.0359 (5)
O10.66864 (16)0.2500−0.27777 (11)0.0501 (5)
O20.81309 (15)0.2500−0.18457 (12)0.0570 (6)
O30.75145 (14)0.25000.29171 (11)0.0559 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0277 (11)0.0469 (15)0.0344 (13)0.000−0.0032 (9)0.000
C20.0283 (11)0.0495 (15)0.0337 (13)0.000−0.0012 (9)0.000
C30.0319 (12)0.0453 (15)0.0328 (13)0.000−0.0006 (9)0.000
C40.0315 (11)0.0347 (13)0.0290 (12)0.000−0.0002 (9)0.000
C50.0373 (12)0.0471 (15)0.0333 (13)0.000−0.0019 (10)0.000
C60.0415 (9)0.0424 (10)0.0418 (10)−0.0048 (8)0.0023 (7)0.0001 (8)
C70.0304 (11)0.0317 (13)0.0310 (12)0.000−0.0015 (9)0.000
C80.0265 (10)0.0332 (13)0.0340 (13)0.000−0.0030 (9)0.000
C90.0312 (11)0.0281 (12)0.0297 (12)0.0000.0014 (9)0.000
C100.0352 (12)0.0387 (14)0.0306 (12)0.000−0.0043 (9)0.000
C110.0279 (11)0.0494 (15)0.0372 (13)0.000−0.0014 (9)0.000
C120.0321 (12)0.0447 (14)0.0322 (13)0.0000.0006 (9)0.000
N10.0355 (11)0.0405 (12)0.0316 (12)0.0000.0020 (8)0.000
O10.0501 (10)0.0725 (14)0.0278 (10)0.000−0.0010 (8)0.000
O20.0322 (9)0.0955 (16)0.0434 (11)0.0000.0058 (8)0.000
O30.0300 (10)0.1027 (17)0.0350 (10)0.000−0.0011 (7)0.000

Geometric parameters (Å, °)

C1—C21.315 (3)C6—H6C0.9800
C1—C71.473 (3)C7—C81.389 (3)
C1—H10.9500C7—C121.393 (3)
C2—C31.493 (3)C8—C91.385 (3)
C2—H20.9500C8—H80.9500
C3—O31.213 (3)C9—C101.376 (3)
C3—C41.530 (3)C9—N11.474 (3)
C4—C51.523 (3)C10—C111.388 (3)
C4—C61.531 (2)C10—H100.9500
C4—C6i1.531 (2)C11—C121.382 (3)
C5—H5A0.9800C11—H110.9500
C5—H5B0.9800C12—H120.9500
C5—H5C0.9800N1—O21.221 (2)
C6—H6A0.9800N1—O11.222 (2)
C6—H6B0.9800
C2—C1—C7127.1 (2)C4—C6—H6C109.5
C2—C1—H1116.5H6A—C6—H6C109.5
C7—C1—H1116.5H6B—C6—H6C109.5
C1—C2—C3121.4 (2)C8—C7—C12118.6 (2)
C1—C2—H2119.3C8—C7—C1118.40 (19)
C3—C2—H2119.3C12—C7—C1123.0 (2)
O3—C3—C2120.9 (2)C9—C8—C7119.27 (19)
O3—C3—C4121.8 (2)C9—C8—H8120.4
C2—C3—C4117.30 (19)C7—C8—H8120.4
C5—C4—C3109.19 (18)C10—C9—C8122.6 (2)
C5—C4—C6110.15 (12)C10—C9—N1118.97 (19)
C3—C4—C6109.36 (12)C8—C9—N1118.42 (18)
C5—C4—C6i110.15 (12)C9—C10—C11117.9 (2)
C3—C4—C6i109.36 (12)C9—C10—H10121.0
C6—C4—C6i108.63 (18)C11—C10—H10121.0
C4—C5—H5A109.5C12—C11—C10120.5 (2)
C4—C5—H5B109.5C12—C11—H11119.8
H5A—C5—H5B109.5C10—C11—H11119.8
C4—C5—H5C109.5C11—C12—C7121.1 (2)
H5A—C5—H5C109.5C11—C12—H12119.4
H5B—C5—H5C109.5C7—C12—H12119.4
C4—C6—H6A109.5O2—N1—O1123.22 (19)
C4—C6—H6B109.5O2—N1—C9118.06 (18)
H6A—C6—H6B109.5O1—N1—C9118.73 (18)
C7—C1—C2—C3180.0C7—C8—C9—C100.0
C1—C2—C3—O30.0C7—C8—C9—N1180.0
C1—C2—C3—C4180.0C8—C9—C10—C110.0
O3—C3—C4—C50.0N1—C9—C10—C11180.0
C2—C3—C4—C5180.0C9—C10—C11—C120.0
O3—C3—C4—C6−120.58 (12)C10—C11—C12—C70.0
C2—C3—C4—C659.42 (12)C8—C7—C12—C110.0
O3—C3—C4—C6i120.58 (12)C1—C7—C12—C11180.0
C2—C3—C4—C6i−59.42 (12)C10—C9—N1—O2180.0
C2—C1—C7—C8180.0C8—C9—N1—O20.0
C2—C1—C7—C120.0C10—C9—N1—O10.0
C12—C7—C8—C90.0C8—C9—N1—O1180.0
C1—C7—C8—C9180.0

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6A···O2ii0.982.443.367 (2)158
C10—H10···O2iii0.952.503.366 (3)152

Symmetry codes: (ii) −x+3/2, −y, z+1/2; (iii) x−1/2, −y+1/2, −z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2958).

References

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