4-[(4-Methyl-phen-yl)amino]-pent-3-en-2-one.

The title enamino-ketone, C(12)H(15)NO, is a derivative of 4-(phenyl-amino)-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 intra-molecular N-H⋯O inter-action and an inter-molecular C-H⋯O hydrogen bond are observed.

Related literature

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

Experimental

Crystal data

C12H15NO

M = 189.25

Monoclinic,

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 ▶) 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 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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 ▶).

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

C12H15NO	F(000) = 408
Mr = 189.25	Dx = 1.214 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8475 reflections
a = 10.0736 (2) Å	θ = 2.9–28.3°
b = 10.8800 (2) Å	µ = 0.08 mm−1
c = 10.0723 (2) Å	T = 100 K
β = 110.291 (1)°	Cuboid, white
V = 1035.43 (3) Å3	0.34 × 0.31 × 0.2 mm
Z = 4

Bruker X8 APEXII 4K Kappa CCD diffractometer	2257 independent reflections
Radiation source: fine-focus sealed tube	2011 reflections with I > 2σ(I)
graphite	Rint = 0.024
ω and φ scans	θmax = 27°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→12
Tmin = 0.974, Tmax = 0.985	k = −13→13
17880 measured reflections	l = −12→12

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0527P)2 + 0.3154P] where P = (Fo2 + 2Fc2)/3
2257 reflections	(Δ/σ)max = 0.001
134 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

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.

	x	y	z	Uiso*/Ueq
H11	0.4680 (15)	0.6492 (15)	0.1245 (16)	0.035 (4)*
C1	0.40618 (11)	0.93113 (10)	0.19271 (12)	0.0217 (2)
H1A	0.3029	0.923	0.1547	0.033*
H1B	0.4343	1.0054	0.1542	0.033*
H1C	0.4381	0.9371	0.2961	0.033*
C2	0.47215 (10)	0.82105 (9)	0.15165 (10)	0.0172 (2)
C3	0.58328 (10)	0.83668 (10)	0.10224 (11)	0.0184 (2)
H3	0.6177	0.9177	0.1004	0.022*
C4	0.64936 (10)	0.73921 (10)	0.05403 (11)	0.0189 (2)
C5	0.76886 (11)	0.77128 (11)	0.00155 (12)	0.0237 (2)
H5A	0.8532	0.7236	0.0543	0.036*
H5B	0.7901	0.8592	0.0158	0.036*
H5C	0.7407	0.7518	−0.0995	0.036*
C111	0.30726 (10)	0.66767 (9)	0.19824 (11)	0.0168 (2)
C112	0.26693 (11)	0.72321 (10)	0.30296 (11)	0.0199 (2)
H112	0.3174	0.7925	0.3529	0.024*
C113	0.15224 (11)	0.67660 (10)	0.33410 (11)	0.0213 (2)
H113	0.1239	0.7164	0.4039	0.026*
C114	0.07814 (10)	0.57364 (10)	0.26603 (11)	0.0197 (2)
C115	0.12396 (11)	0.51612 (10)	0.16576 (11)	0.0206 (2)
H115	0.0773	0.4437	0.1203	0.025*
C116	0.23603 (11)	0.56237 (10)	0.13106 (11)	0.0194 (2)
H116	0.2644	0.5223	0.0614	0.023*
C117	−0.04840 (11)	0.52533 (11)	0.29731 (13)	0.0257 (3)
H11A	−0.0518	0.5634	0.3843	0.039*
H11B	−0.0404	0.436	0.3095	0.039*
H11C	−0.1351	0.5453	0.2184	0.039*
N11	0.42309 (9)	0.70705 (8)	0.15977 (9)	0.0176 (2)
O12	0.61277 (8)	0.62890 (7)	0.05166 (8)	0.0227 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0245 (5)	0.0165 (5)	0.0269 (5)	0.0011 (4)	0.0124 (4)	−0.0005 (4)
C2	0.0182 (5)	0.0165 (5)	0.0155 (5)	0.0009 (4)	0.0042 (4)	0.0003 (4)
C3	0.0191 (5)	0.0164 (5)	0.0196 (5)	−0.0013 (4)	0.0068 (4)	0.0002 (4)
C4	0.0174 (5)	0.0206 (5)	0.0185 (5)	0.0000 (4)	0.0059 (4)	0.0013 (4)
C5	0.0212 (5)	0.0240 (6)	0.0292 (6)	−0.0016 (4)	0.0127 (4)	0.0002 (4)
C111	0.0156 (4)	0.0167 (5)	0.0182 (5)	0.0028 (4)	0.0061 (4)	0.0035 (4)
C112	0.0216 (5)	0.0191 (5)	0.0191 (5)	−0.0010 (4)	0.0073 (4)	−0.0016 (4)
C113	0.0224 (5)	0.0238 (6)	0.0207 (5)	0.0029 (4)	0.0114 (4)	0.0000 (4)
C114	0.0162 (5)	0.0215 (5)	0.0216 (5)	0.0032 (4)	0.0069 (4)	0.0048 (4)
C115	0.0193 (5)	0.0188 (5)	0.0229 (5)	−0.0012 (4)	0.0062 (4)	−0.0006 (4)
C116	0.0205 (5)	0.0189 (5)	0.0200 (5)	0.0024 (4)	0.0087 (4)	−0.0005 (4)
C117	0.0200 (5)	0.0289 (6)	0.0313 (6)	0.0002 (4)	0.0129 (4)	0.0035 (5)
N11	0.0182 (4)	0.0156 (4)	0.0214 (4)	0.0016 (3)	0.0100 (3)	0.0002 (3)
O12	0.0245 (4)	0.0171 (4)	0.0306 (4)	0.0000 (3)	0.0145 (3)	−0.0006 (3)

C1—C2	1.4959 (14)	C111—N11	1.4173 (13)
C1—H1A	0.98	C112—C113	1.3934 (14)
C1—H1B	0.98	C112—H112	0.95
C1—H1C	0.98	C113—C114	1.3882 (16)
C2—N11	1.3482 (13)	C113—H113	0.95
C2—C3	1.3842 (14)	C114—C115	1.3957 (15)
C3—C4	1.4240 (15)	C114—C117	1.5097 (14)
C3—H3	0.95	C115—C116	1.3870 (14)
C4—O12	1.2533 (13)	C115—H115	0.95
C4—C5	1.5138 (14)	C116—H116	0.95
C5—H5A	0.98	C117—H11A	0.98
C5—H5B	0.98	C117—H11B	0.98
C5—H5C	0.98	C117—H11C	0.98
C111—C112	1.3929 (14)	N11—H11	0.916 (16)
C111—C116	1.3958 (15)
C2—C1—H1A	109.5	C111—C112—C113	119.66 (10)
C2—C1—H1B	109.5	C111—C112—H112	120.2
H1A—C1—H1B	109.5	C113—C112—H112	120.2
C2—C1—H1C	109.5	C114—C113—C112	121.89 (10)
H1A—C1—H1C	109.5	C114—C113—H113	119.1
H1B—C1—H1C	109.5	C112—C113—H113	119.1
N11—C2—C3	119.61 (9)	C113—C114—C115	117.59 (9)
N11—C2—C1	120.83 (9)	C113—C114—C117	121.75 (10)
C3—C2—C1	119.56 (9)	C115—C114—C117	120.66 (10)
C2—C3—C4	124.27 (10)	C116—C115—C114	121.46 (10)
C2—C3—H3	117.9	C116—C115—H115	119.3
C4—C3—H3	117.9	C114—C115—H115	119.3
O12—C4—C3	123.40 (9)	C115—C116—C111	120.14 (10)
O12—C4—C5	118.58 (9)	C115—C116—H116	119.9
C3—C4—C5	118.02 (9)	C111—C116—H116	119.9
C4—C5—H5A	109.5	C114—C117—H11A	109.5
C4—C5—H5B	109.5	C114—C117—H11B	109.5
H5A—C5—H5B	109.5	H11A—C117—H11B	109.5
C4—C5—H5C	109.5	C114—C117—H11C	109.5
H5A—C5—H5C	109.5	H11A—C117—H11C	109.5
H5B—C5—H5C	109.5	H11B—C117—H11C	109.5
C112—C111—C116	119.16 (9)	C2—N11—C111	130.44 (9)
C112—C111—N11	124.05 (9)	C2—N11—H11	111.6 (9)
C116—C111—N11	116.69 (9)	C111—N11—H11	117.5 (9)
N11—C2—C3—C4	1.92 (15)	C113—C114—C115—C116	−2.38 (16)
C1—C2—C3—C4	−176.91 (9)	C117—C114—C115—C116	177.08 (10)
C2—C3—C4—O12	0.03 (16)	C114—C115—C116—C111	0.96 (16)
C2—C3—C4—C5	179.34 (9)	C112—C111—C116—C115	1.83 (15)
C116—C111—C112—C113	−3.10 (15)	N11—C111—C116—C115	178.26 (9)
N11—C111—C112—C113	−179.26 (9)	C3—C2—N11—C111	−175.93 (9)
C111—C112—C113—C114	1.67 (16)	C1—C2—N11—C111	2.88 (16)
C112—C113—C114—C115	1.06 (16)	C112—C111—N11—C2	−36.50 (16)
C112—C113—C114—C117	−178.39 (10)	C116—C111—N11—C2	147.26 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C116—H116···O12i	0.95	2.55	3.462 (1)	160
N11—H11···O12	0.916 (16)	1.859 (16)	2.6463 (13)	142.7 (15)

Parameter	I	II	III	IV
N11—C111	1.417 (2)	1.422 (2)	1.521 (4)/1.463 (3)	1.440 (4)
N11—C2	1.348 (1)	1.345 (2)	1.320 (4)	1.319 (4)
O12—C4	1.253 (1)	1.257 (2)	1.290 (3)	1.291 (4)
C2—C3	1.384 (2)	1.383 (3)	1.410 (4)	1.423 (4)
C3—C4	1.424 (2)	1.420 (2)	1.365 (3)	1.382 (3)
N11···O12	2.646 (1)	2.635 (2)	2.885 (3)	2.886 (3)
N11—C2—C4—O12	1.70 (9)	-0.5 (1)	4.1 (2)	-2.6 (2)
Dihedral angle	29.90 (3)	49.53 (5)	87.47 (4)/89.36 (8)	85.58 (8)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C116—H116⋯O12i	0.95	2.55	3.462 (1)	160
N11—H11⋯O12	0.916 (16)	1.859 (16)	2.6463 (13)	142.7 (15)

Symmetry code: (i) .

Table 2

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

Parameter	I	II	III	IV
N11—C111	1.417 (2)	1.422 (2)	1.521 (4)/1.463 (3)	1.440 (4)
N11—C2	1.348 (1)	1.345 (2)	1.320 (4)	1.319 (4)
O12—C4	1.253 (1)	1.257 (2)	1.290 (3)	1.291 (4)
C2—C3	1.384 (2)	1.383 (3)	1.410 (4)	1.423 (4)
C3—C4	1.424 (2)	1.420 (2)	1.365 (3)	1.382 (3)
N11⋯O12	2.646 (1)	2.635 (2)	2.885 (3)	2.886 (3)
N11—C2—C4—O12	1.70 (9)	−0.5 (1)	4.1 (2)	−2.6 (2)
Dihedral angle	29.90 (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-one (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.