4-(2,3-Dimethyl­anilino)pent-3-en-2-one

Gertruida J S Venter; Gideon Steyl; Andreas Roodt

doi:10.1107/S1600536812038779

. 2012 Sep 15;68(Pt 10):o2930–o2931. doi: 10.1107/S1600536812038779

4-(2,3-Dimethylanilino)pent-3-en-2-one

Gertruida J S Venter ^a,^*, Gideon Steyl ^a, Andreas Roodt ^a

PMCID: PMC3470305 PMID: 23125718

Abstract

In the title compound, C₁₃H₁₇NO, the dihedral angle between the aryl ring and the aminoacrylaldehyde mean plane [N—C=C—C=O; maximum deviation = 0.0144 (9) Å] is 53.43 (4)°. There is an intramolecular N—H⋯O hydrogen bond involving the amine and carbonyl groups. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming chains propagating along [001].

Related literature

For background to the synthesis of the title compound, see: Shaheen et al. (2006 ▶); Venter et al. (2010 ▶). For applications of rhodium compounds containing bidentate ligand systems, see: Pyżuk et al. (1993 ▶); Tan et al. (2008 ▶); Xia et al. (2008 ▶). For related rhodium enaminoketonato complexes, see: Brink et al. (2010 ▶); Damoense et al. (1994 ▶); Roodt & Steyn (2000 ▶); Venter et al. (2009a ▶,b ▶; 2012 ▶).

Experimental

Crystal data

C₁₃H₁₇NO
M _r = 203.28
Monoclinic,
a = 7.526 (3) Å
b = 12.450 (5) Å
c = 12.040 (4) Å
β = 90.243 (4)°
V = 1128.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.18 × 0.16 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.987, T _max = 0.994
20265 measured reflections
2817 independent reflections
2528 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.103
S = 1.05
2817 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SIR92 (Altomare et al., 1992) ▶; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812038779/su2465sup1.cif

e-68-o2930-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038779/su2465Isup2.hkl

e-68-o2930-Isup2.hkl^{(135.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812038779/su2465Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.911 (15)	1.869 (15)	2.6348 (13)	140.2 (13)
C1—H1A⋯O1ⁱ	0.98	2.49	3.4599 (15)	173

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

Dr Tania Hill is thanked for the XRD data collection. Financial assistance from the University of the Free State Strategic Academic Cluster Initiative, SASOL, the South African National Research Foundation (SA-NRF/THRIP) and the Inkaba yeAfrika Research Initiative is gratefully acknowledged. 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

The β-diketone compound AcacH (acetylacetone; or when coordinated acetylacetonato, acac^-) has been studied extensively, with a multitude of derivatives synthesized to date. One such derivative type, known as enaminoketones, containing N and O atoms as well as an unsaturated C═C bond, and are of interest in various fields including liquid crystals (Pyżuk et al., 1993) and fluorescence studies (Xia et al., 2008). They also have significant application possibilities in medicine (Tan et al., 2008)] and catalysis (Roodt & Steyn, 2000; Brink et al., 2010).

The title compound (Fig. 1) is an enaminoketone derivative of 4-(phenylamino)pent-3-en-2-one (Shaheen et al., 2006). Bond distances in the the title compound differ significantly from those in compounds where the ligand is coordinated to rhodium (Venter et al., 2009a,b; 2012); Damoense et al., 1994), but it share characteristics with other enaminoketones of this type (Venter et al., 2010). The C2–C3 bond distance of 1.3849 (14) Å versus the C3–C4 distance of 1.4251 (13) Å indicates an unsaturated bond in the pentenone backbone. Here the intramolecular distance N1···O1 is 2.6348 (13) Å which is considerably less (~ 0.2 Å) than that observed when the ligand is coordinated to rhodium for example (Venter et al., 2009a,b; 2012; Damoense et al., 1994).

The intramolecular N-H···O hydrogen bond that is formed (Fig. 1 and Table 1) enhances the planarity of the aminopentenone moiety. The aminoacrylaldehyde mean plane [N1-C2═C3-C4═O1; maximum deviation = 0.0144 (9) Å] makes a dihedral angle of 53.43 (4)° with the C11-C16 benzene ring. This angle is dependent on the position of the substituents on the aromatic ring. Compounds with substituents in the ortho positions result in larger dihedral angles, while smaller angles are found for derivatives with substituents in the para position (Venter et al., 2009a,b; 2012).

In the crystal, there are C-H···O hydrogen bonds leading to the formation of chains propagating along [001] (Table 1 and Fig. 2).

Experimental

The title compound was prepared following the literature procedure (Shaheen et al., 2006; Venter et al., 2010).