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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o3011–o3012.
Published online 2010 October 31. doi:  10.1107/S1600536810043680
PMCID: PMC3009096

4-[(4-Methyl­phen­yl)amino]­pent-3-en-2-one

Abstract

The title enamino­ketone, C12H15NO, is a derivative of 4-(phenyl­amino)­pent-3-en-2-one with an approximately planar pentenone backbone, the greatest displacement from the plane being 0.042 (1) Å; the asymmetry in C—C distances in the group suggests the presence of unsaturated bonds. The dihedral angle between the benzene ring and the pentenone plane is 29.90 (4)°. In the crystal, an intra­molecular N—H(...)O inter­action and an inter­molecular C—H(...)O hydrogen bond are observed.

Related literature

For synthetic background, see: Shaheen et al. (2006 [triangle]); Venter et al. (2010 [triangle]). For applications of enamino­ketones, see: Brink et al. (2010 [triangle]); Chen & Rhodes (1996 [triangle]); Pyżuk et al. (1993 [triangle]); Roodt & Steyn (2000 [triangle]); Tan et al. (2008 [triangle]); Xia et al. (2008 [triangle]). For structures of related ligand systems, see: Venter et al. (2009a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3011-scheme1.jpg

Experimental

Crystal data

  • C12H15NO
  • M r = 189.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3011-efi1.jpg
  • a = 10.0736 (2) Å
  • b = 10.8800 (2) Å
  • c = 10.0723 (2) Å
  • β = 110.291 (1)°
  • V = 1035.43 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 100 K
  • 0.34 × 0.31 × 0.2 mm

Data collection

  • Bruker X8 APEXII 4K Kappa CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2004 [triangle]) T min = 0.974, T max = 0.985
  • 17880 measured reflections
  • 2257 independent reflections
  • 2011 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.099
  • S = 1.05
  • 2257 reflections
  • 134 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT-Plus (Bruker, 2004 [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: DIAMOND (Brandenburg & Putz, 2005 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)
Table 2
Comparative geometric parameters (Å, °) for free and coordinated N,O-bidendate (N,O-bid) compounds

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043680/is2620sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043680/is2620Isup2.hkl

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

Acknowledgments

Financial assistance from the University of the Free State is gratefully acknowledged. The authors also express their gratitude to SASOL and the South African National Research Foundation (SA-NRF/THRIP) for financial support of this project. Part of this material is based on work supported by the SA-NRF/THRIP under grant No. GUN 2068915. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the SA-NRF.

supplementary crystallographic information

Comment

A well known system in organometallic chemistry is the β-diketone compound AcacH (acetylacetone; or when coordinated acetylacetonato, acac-). A multitude of derivatives have been synthesized to date, with enaminoketones being one type. Since enaminoketones contain N and O atoms as well as an unsaturated C—C bond, these electron-rich compounds are of interest in various fields including liquid crystals (Pyżuk et al., 1993), fluorescence studies (Xia et al., 2008) as well as formation of complexes of medical interest (Tan et al., 2008; Chen & Rhodes, 1996). It also has significant application possibilities in catalysis (Roodt & Steyn, 2000; Brink et al., 2010).

The title compound (Fig. 1) crystallizes in the monoclinic space group P21/c with Z = 4. This enaminoketone is a derivative of 4-(phenylamino)pent-3-en-2-one (PhonyH; Shaheen et al., 2006). Bond distances differ significantly from compounds coordinated to rhodium (Table 2; Venter et al., 2009a,b), such as the distance, N1···O1, greatly increasing (~0.2 Å) upon coordination to the metal. Similarities in bond parameters to other uncoordinated enaminoketone compounds (Venter et al., 2010) were observed. The C2—C3 distance of 1.385 (2) Å, versus the C3—C4 bond distance of 1.424 (2) Å indicates an unsaturated bond in the pentenone backbone. The dihedral angle between the benzene ring and the pentenone plane is 29.90 (4)°.

Experimental

A solution of acetylacetone (11.02 g, 0.1101 mol), 4-Me-aniline (10.83 g, 0.1010 mol) and 2 drops of H2SO4 (conc.) in 150 ml benzene was refluxed for 24 h in a Dean–Stark trap, filtered and left to crystallize. Crystals suitable for X-ray diffraction were obtained in 16.95 g (88.67%) yield. This compound is stable in air and light over a period of several months.

Refinement

The methyl and aromatic H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 and 0.98 Å and Uiso(H) = 1.5Ueq(C) and 1.2Ueq(C), respectively. The methyl groups were generated to fit the difference electron density and the groups were then refined as rigid rotors. The highest residual electron-density peak is 0.74 Å from C5.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability displacement level.

Crystal data

C12H15NOF(000) = 408
Mr = 189.25Dx = 1.214 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8475 reflections
a = 10.0736 (2) Åθ = 2.9–28.3°
b = 10.8800 (2) ŵ = 0.08 mm1
c = 10.0723 (2) ÅT = 100 K
β = 110.291 (1)°Cuboid, white
V = 1035.43 (3) Å30.34 × 0.31 × 0.2 mm
Z = 4

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer2257 independent reflections
Radiation source: fine-focus sealed tube2011 reflections with I > 2σ(I)
graphiteRint = 0.024
ω and [var phi] scansθmax = 27°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −9→12
Tmin = 0.974, Tmax = 0.985k = −13→13
17880 measured reflectionsl = −12→12

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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0527P)2 + 0.3154P] where P = (Fo2 + 2Fc2)/3
2257 reflections(Δ/σ)max = 0.001
134 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.19 e Å3

Special details

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 30 s/frame. A total of 688 frames were collected with a frame width of 0.5° covering up to θ = 27.00° with 99.9% completeness accomplished.
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
H110.4680 (15)0.6492 (15)0.1245 (16)0.035 (4)*
C10.40618 (11)0.93113 (10)0.19271 (12)0.0217 (2)
H1A0.30290.9230.15470.033*
H1B0.43431.00540.15420.033*
H1C0.43810.93710.29610.033*
C20.47215 (10)0.82105 (9)0.15165 (10)0.0172 (2)
C30.58328 (10)0.83668 (10)0.10224 (11)0.0184 (2)
H30.61770.91770.10040.022*
C40.64936 (10)0.73921 (10)0.05403 (11)0.0189 (2)
C50.76886 (11)0.77128 (11)0.00155 (12)0.0237 (2)
H5A0.85320.72360.05430.036*
H5B0.79010.85920.01580.036*
H5C0.74070.7518−0.09950.036*
C1110.30726 (10)0.66767 (9)0.19824 (11)0.0168 (2)
C1120.26693 (11)0.72321 (10)0.30296 (11)0.0199 (2)
H1120.31740.79250.35290.024*
C1130.15224 (11)0.67660 (10)0.33410 (11)0.0213 (2)
H1130.12390.71640.40390.026*
C1140.07814 (10)0.57364 (10)0.26603 (11)0.0197 (2)
C1150.12396 (11)0.51612 (10)0.16576 (11)0.0206 (2)
H1150.07730.44370.12030.025*
C1160.23603 (11)0.56237 (10)0.13106 (11)0.0194 (2)
H1160.26440.52230.06140.023*
C117−0.04840 (11)0.52533 (11)0.29731 (13)0.0257 (3)
H11A−0.05180.56340.38430.039*
H11B−0.04040.4360.30950.039*
H11C−0.13510.54530.21840.039*
N110.42309 (9)0.70705 (8)0.15977 (9)0.0176 (2)
O120.61277 (8)0.62890 (7)0.05166 (8)0.0227 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0245 (5)0.0165 (5)0.0269 (5)0.0011 (4)0.0124 (4)−0.0005 (4)
C20.0182 (5)0.0165 (5)0.0155 (5)0.0009 (4)0.0042 (4)0.0003 (4)
C30.0191 (5)0.0164 (5)0.0196 (5)−0.0013 (4)0.0068 (4)0.0002 (4)
C40.0174 (5)0.0206 (5)0.0185 (5)0.0000 (4)0.0059 (4)0.0013 (4)
C50.0212 (5)0.0240 (6)0.0292 (6)−0.0016 (4)0.0127 (4)0.0002 (4)
C1110.0156 (4)0.0167 (5)0.0182 (5)0.0028 (4)0.0061 (4)0.0035 (4)
C1120.0216 (5)0.0191 (5)0.0191 (5)−0.0010 (4)0.0073 (4)−0.0016 (4)
C1130.0224 (5)0.0238 (6)0.0207 (5)0.0029 (4)0.0114 (4)0.0000 (4)
C1140.0162 (5)0.0215 (5)0.0216 (5)0.0032 (4)0.0069 (4)0.0048 (4)
C1150.0193 (5)0.0188 (5)0.0229 (5)−0.0012 (4)0.0062 (4)−0.0006 (4)
C1160.0205 (5)0.0189 (5)0.0200 (5)0.0024 (4)0.0087 (4)−0.0005 (4)
C1170.0200 (5)0.0289 (6)0.0313 (6)0.0002 (4)0.0129 (4)0.0035 (5)
N110.0182 (4)0.0156 (4)0.0214 (4)0.0016 (3)0.0100 (3)0.0002 (3)
O120.0245 (4)0.0171 (4)0.0306 (4)0.0000 (3)0.0145 (3)−0.0006 (3)

Geometric parameters (Å, °)

C1—C21.4959 (14)C111—N111.4173 (13)
C1—H1A0.98C112—C1131.3934 (14)
C1—H1B0.98C112—H1120.95
C1—H1C0.98C113—C1141.3882 (16)
C2—N111.3482 (13)C113—H1130.95
C2—C31.3842 (14)C114—C1151.3957 (15)
C3—C41.4240 (15)C114—C1171.5097 (14)
C3—H30.95C115—C1161.3870 (14)
C4—O121.2533 (13)C115—H1150.95
C4—C51.5138 (14)C116—H1160.95
C5—H5A0.98C117—H11A0.98
C5—H5B0.98C117—H11B0.98
C5—H5C0.98C117—H11C0.98
C111—C1121.3929 (14)N11—H110.916 (16)
C111—C1161.3958 (15)
C2—C1—H1A109.5C111—C112—C113119.66 (10)
C2—C1—H1B109.5C111—C112—H112120.2
H1A—C1—H1B109.5C113—C112—H112120.2
C2—C1—H1C109.5C114—C113—C112121.89 (10)
H1A—C1—H1C109.5C114—C113—H113119.1
H1B—C1—H1C109.5C112—C113—H113119.1
N11—C2—C3119.61 (9)C113—C114—C115117.59 (9)
N11—C2—C1120.83 (9)C113—C114—C117121.75 (10)
C3—C2—C1119.56 (9)C115—C114—C117120.66 (10)
C2—C3—C4124.27 (10)C116—C115—C114121.46 (10)
C2—C3—H3117.9C116—C115—H115119.3
C4—C3—H3117.9C114—C115—H115119.3
O12—C4—C3123.40 (9)C115—C116—C111120.14 (10)
O12—C4—C5118.58 (9)C115—C116—H116119.9
C3—C4—C5118.02 (9)C111—C116—H116119.9
C4—C5—H5A109.5C114—C117—H11A109.5
C4—C5—H5B109.5C114—C117—H11B109.5
H5A—C5—H5B109.5H11A—C117—H11B109.5
C4—C5—H5C109.5C114—C117—H11C109.5
H5A—C5—H5C109.5H11A—C117—H11C109.5
H5B—C5—H5C109.5H11B—C117—H11C109.5
C112—C111—C116119.16 (9)C2—N11—C111130.44 (9)
C112—C111—N11124.05 (9)C2—N11—H11111.6 (9)
C116—C111—N11116.69 (9)C111—N11—H11117.5 (9)
N11—C2—C3—C41.92 (15)C113—C114—C115—C116−2.38 (16)
C1—C2—C3—C4−176.91 (9)C117—C114—C115—C116177.08 (10)
C2—C3—C4—O120.03 (16)C114—C115—C116—C1110.96 (16)
C2—C3—C4—C5179.34 (9)C112—C111—C116—C1151.83 (15)
C116—C111—C112—C113−3.10 (15)N11—C111—C116—C115178.26 (9)
N11—C111—C112—C113−179.26 (9)C3—C2—N11—C111−175.93 (9)
C111—C112—C113—C1141.67 (16)C1—C2—N11—C1112.88 (16)
C112—C113—C114—C1151.06 (16)C112—C111—N11—C2−36.50 (16)
C112—C113—C114—C117−178.39 (10)C116—C111—N11—C2147.26 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C116—H116···O12i0.952.553.462 (1)160
N11—H11···O120.916 (16)1.859 (16)2.6463 (13)142.7 (15)

Symmetry codes: (i) −x+1, −y+1, −z.

Table 2 Comparative geometric parameters (Å, °) for free and coordinated N,O-bidendate (N,O-bid) compounds

ParameterIIIIIIIV
N11—C1111.417 (2)1.422 (2)1.521 (4)/1.463 (3)1.440 (4)
N11—C21.348 (1)1.345 (2)1.320 (4)1.319 (4)
O12—C41.253 (1)1.257 (2)1.290 (3)1.291 (4)
C2—C31.384 (2)1.383 (3)1.410 (4)1.423 (4)
C3—C41.424 (2)1.420 (2)1.365 (3)1.382 (3)
N11···O122.646 (1)2.635 (2)2.885 (3)2.886 (3)
N11—C2—C4—O121.70 (9)-0.5 (1)4.1 (2)-2.6 (2)
Dihedral angle29.90 (3)49.53 (5)87.47 (4)/89.36 (8)85.58 (8)

(I) This work. (II) Uncoordinated 4-(2-methylphenylamino)pent-3-en-2-onato (Venter et al., 2010). (III) N,O-bid = 4-(2,3-dimethylphenylamino)pent-3-en-2-onato (Venter et al., 2009a). (IV) N,O-bid = 4-(2,6-dimethylphenylamino)pent-3-en-2-onato (Venter et al., 2009b). The dihedral angle is defined as the torsion angle between the N—C—C—C—O plane and the phenyl ring. A positive angle denotes a clockwise rotation.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2620).

References

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