4-(2-Methyl-anilino)pent-3-en-2-one.

The title enamino ketone, C(12)H(15)NO, a derivative of 4-(phenyl-amino)-pent-3-en-2-one, presents a roughly planar [greatest displacement of an atom from the pentenone plane is 0.033 (2) Å] pentenone backbone, enhanced by an intra-molecular N-H⋯O hydrogen bond; the asymmetry in C-C distances in the group suggests the presence of unsaturated bonds. The overall geometry in the free ligand differs significantly from that in other reported compounds, in which it is coordinated to rhodium; this is reflected in the bond distances [the N⋯O distance is significantly increased (0.2 Å) upon coordination to the metal] and the dihedral angle between the benzene ring and the pentenone backbone [49.53 (5)°]. All of the methyl goups are rotationally disordered over two orientations of equal occupancy.

Related literature

For synthetic background, see: Shaheen et al. (2006 ▶). For applications of enamino­ketones in liquid crystals, see: Pyżuk et al. (1993 ▶), in fluorescence, see: Xia et al. (2008 ▶), in complexes of medical inter­est, see: Tan et al. (2008 ▶); Chen & Rhodes (1996 ▶), in catalysis, see: Nair et al. (2002 ▶); Van Aswegen et al. (1991 ▶); Steyn et al. (1992 ▶, 1997 ▶); Otto et al. (1998 ▶); Roodt & Steyn (2000 ▶); Brink et al. (2010 ▶). For the structures of related ligand systems, see: Damoense et al. (1994 ▶); Venter et al. (2009a ▶,b ▶).

Experimental

Crystal data

C12H15NO

M = 189.25

Monoclinic,

a = 7.5674 (7) Å

b = 11.5075 (9) Å

c = 12.0996 (11) Å

β = 92.154 (5)°

V = 1052.91 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.55 × 0.23 × 0.12 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.960, T max = 0.991

10022 measured reflections

2308 independent reflections

1854 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.150

S = 1.07

2308 reflections

129 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.35 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/S1600536810021045/bg2348sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021045/bg2348Isup2.hkl

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

C12H15NO	F(000) = 408
Mr = 189.25	Dx = 1.194 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2889 reflections
a = 7.5674 (7) Å	θ = 2.7–28.2°
b = 11.5075 (9) Å	µ = 0.08 mm−1
c = 12.0996 (11) Å	T = 100 K
β = 92.154 (5)°	Plate, colourless
V = 1052.91 (16) Å3	0.55 × 0.23 × 0.12 mm
Z = 4

Bruker X8 APEXII 4K Kappa CCD diffractometer	2308 independent reflections
Radiation source: fine-focus sealed tube	1854 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω and φ scans	θmax = 27°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→9
Tmin = 0.960, Tmax = 0.991	k = −14→12
10022 measured reflections	l = −15→15

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0654P)2 + 0.9506P] where P = (Fo2 + 2Fc2)/3
2308 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 60 seconds/frame. A total of 688 frames were collected with a frame width of 0.5° covering up to θ = 28.24° with 99.1% 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	Occ. (<1)
C1	0.4288 (3)	0.30725 (17)	0.73241 (16)	0.0212 (4)
H1A	0.4068	0.3907	0.723	0.032*	0.5
H1B	0.3886	0.2659	0.6653	0.032*	0.5
H1C	0.5557	0.2939	0.7458	0.032*	0.5
H1D	0.4939	0.243	0.6998	0.032*	0.5
H1E	0.5121	0.3678	0.7575	0.032*	0.5
H1F	0.345	0.3397	0.6769	0.032*	0.5
C2	0.3300 (2)	0.26340 (16)	0.82877 (15)	0.0172 (4)
C3	0.3410 (2)	0.14730 (15)	0.85770 (15)	0.0174 (4)
H3	0.4142	0.0982	0.8159	0.021*
C4	0.2494 (2)	0.09702 (15)	0.94616 (14)	0.0162 (4)
C5	0.2647 (3)	−0.03183 (16)	0.96633 (16)	0.0217 (4)
H5A	0.1945	−0.0532	1.0296	0.033*	0.5
H5B	0.3889	−0.0521	0.982	0.033*	0.5
H5C	0.2208	−0.0739	0.9005	0.033*	0.5
H5D	0.3417	−0.0663	0.9118	0.033*	0.5
H5E	0.1472	−0.0674	0.9594	0.033*	0.5
H5F	0.3153	−0.0456	1.0409	0.033*	0.5
C12	0.2730 (3)	0.49042 (17)	1.07167 (15)	0.0218 (4)
H12A	0.2961	0.4067	1.0685	0.033*	0.5
H12B	0.1797	0.5055	1.1238	0.033*	0.5
H12C	0.3812	0.5311	1.0964	0.033*	0.5
H12D	0.2752	0.5555	1.1239	0.033*	0.5
H12E	0.3917	0.4567	1.0687	0.033*	0.5
H12F	0.1901	0.4311	1.0961	0.033*	0.5
O12	0.15430 (17)	0.15514 (11)	1.00878 (10)	0.0195 (3)
C111	0.1994 (2)	0.45704 (15)	0.86788 (15)	0.0160 (4)
C112	0.2147 (2)	0.53330 (16)	0.95849 (15)	0.0172 (4)
C113	0.1737 (2)	0.64979 (16)	0.94050 (16)	0.0203 (4)
H113	0.1821	0.7026	1.0008	0.024*
C114	0.1207 (2)	0.69078 (16)	0.83647 (16)	0.0208 (4)
H114	0.0932	0.7707	0.8262	0.025*
C115	0.1081 (2)	0.61469 (16)	0.74784 (15)	0.0192 (4)
H115	0.0738	0.6426	0.6763	0.023*
C116	0.1456 (2)	0.49751 (16)	0.76367 (15)	0.0180 (4)
H116	0.1344	0.445	0.7032	0.022*
N11	0.2320 (2)	0.33691 (13)	0.88747 (13)	0.0176 (3)
H11	0.1801	0.3060	0.9471	0.021*

	U11	U22	U33	U12	U13	U23
C1	0.0225 (9)	0.0206 (9)	0.0210 (9)	0.0019 (7)	0.0057 (7)	0.0032 (7)
C2	0.0167 (8)	0.0190 (9)	0.0159 (9)	0.0001 (7)	0.0001 (7)	−0.0007 (7)
C3	0.0192 (9)	0.0163 (9)	0.0168 (9)	0.0028 (7)	0.0029 (7)	−0.0015 (7)
C4	0.0176 (8)	0.0157 (9)	0.0152 (8)	0.0008 (7)	−0.0013 (7)	−0.0010 (7)
C5	0.0254 (10)	0.0152 (9)	0.0250 (10)	0.0014 (7)	0.0062 (8)	0.0005 (7)
C12	0.0221 (9)	0.0244 (10)	0.0188 (9)	−0.0010 (8)	0.0000 (7)	−0.0015 (7)
O12	0.0254 (7)	0.0157 (6)	0.0176 (7)	0.0015 (5)	0.0051 (5)	−0.0001 (5)
C111	0.0158 (8)	0.0122 (8)	0.0202 (9)	−0.0008 (6)	0.0032 (7)	0.0003 (7)
C112	0.0164 (8)	0.0177 (9)	0.0177 (9)	−0.0018 (7)	0.0023 (7)	−0.0002 (7)
C113	0.0222 (9)	0.0170 (9)	0.0220 (9)	−0.0018 (7)	0.0033 (7)	−0.0059 (7)
C114	0.0214 (9)	0.0129 (8)	0.0284 (10)	0.0004 (7)	0.0047 (8)	0.0012 (7)
C115	0.0189 (9)	0.0190 (9)	0.0198 (9)	−0.0001 (7)	0.0024 (7)	0.0031 (7)
C116	0.0200 (9)	0.0163 (9)	0.0178 (9)	−0.0020 (7)	0.0020 (7)	−0.0018 (7)
N11	0.0232 (8)	0.0132 (7)	0.0168 (8)	0.0009 (6)	0.0053 (6)	0.0012 (6)

C1—C2	1.496 (2)	C12—C112	1.506 (3)
C1—H1A	0.98	C12—H12A	0.98
C1—H1B	0.98	C12—H12B	0.98
C1—H1C	0.98	C12—H12C	0.98
C1—H1D	0.98	C12—H12D	0.98
C1—H1E	0.98	C12—H12E	0.98
C1—H1F	0.98	C12—H12F	0.98
C2—N11	1.345 (2)	C111—C116	1.391 (3)
C2—C3	1.383 (3)	C111—C112	1.406 (3)
C3—C4	1.420 (2)	C111—N11	1.422 (2)
C3—H3	0.95	C112—C113	1.391 (3)
C4—O12	1.257 (2)	C113—C114	1.389 (3)
C4—C5	1.506 (2)	C113—H113	0.95
C5—H5A	0.98	C114—C115	1.385 (3)
C5—H5B	0.98	C114—H114	0.95
C5—H5C	0.98	C115—C116	1.390 (3)
C5—H5D	0.98	C115—H115	0.95
C5—H5E	0.98	C116—H116	0.95
C5—H5F	0.98	N11—H11	0.9071
C2—C1—H1A	109.5	H5B—C5—H5F	56.3
C2—C1—H1B	109.5	H5C—C5—H5F	141.1
H1A—C1—H1B	109.5	H5D—C5—H5F	109.5
C2—C1—H1C	109.5	H5E—C5—H5F	109.5
H1A—C1—H1C	109.5	C112—C12—H12A	109.5
H1B—C1—H1C	109.5	C112—C12—H12B	109.5
C2—C1—H1D	109.5	H12A—C12—H12B	109.5
H1A—C1—H1D	141.1	C112—C12—H12C	109.5
H1B—C1—H1D	56.3	H12A—C12—H12C	109.5
H1C—C1—H1D	56.3	H12B—C12—H12C	109.5
C2—C1—H1E	109.5	C112—C12—H12D	109.5
H1A—C1—H1E	56.3	H12A—C12—H12D	141.1
H1B—C1—H1E	141.1	H12B—C12—H12D	56.3
H1C—C1—H1E	56.3	H12C—C12—H12D	56.3
H1D—C1—H1E	109.5	C112—C12—H12E	109.5
C2—C1—H1F	109.5	H12A—C12—H12E	56.3
H1A—C1—H1F	56.3	H12B—C12—H12E	141.1
H1B—C1—H1F	56.3	H12C—C12—H12E	56.3
H1C—C1—H1F	141.1	H12D—C12—H12E	109.5
H1D—C1—H1F	109.5	C112—C12—H12F	109.5
H1E—C1—H1F	109.5	H12A—C12—H12F	56.3
N11—C2—C3	120.21 (16)	H12B—C12—H12F	56.3
N11—C2—C1	120.06 (16)	H12C—C12—H12F	141.1
C3—C2—C1	119.73 (16)	H12D—C12—H12F	109.5
C2—C3—C4	123.91 (16)	H12E—C12—H12F	109.5
C2—C3—H3	118	C116—C111—C112	120.72 (16)
C4—C3—H3	118	C116—C111—N11	121.30 (16)
O12—C4—C3	122.97 (16)	C112—C111—N11	117.91 (16)
O12—C4—C5	117.93 (16)	C113—C112—C111	117.91 (17)
C3—C4—C5	119.10 (15)	C113—C112—C12	120.93 (16)
C4—C5—H5A	109.5	C111—C112—C12	121.16 (16)
C4—C5—H5B	109.5	C114—C113—C112	121.61 (17)
H5A—C5—H5B	109.5	C114—C113—H113	119.2
C4—C5—H5C	109.5	C112—C113—H113	119.2
H5A—C5—H5C	109.5	C115—C114—C113	119.74 (17)
H5B—C5—H5C	109.5	C115—C114—H114	120.1
C4—C5—H5D	109.5	C113—C114—H114	120.1
H5A—C5—H5D	141.1	C114—C115—C116	119.93 (17)
H5B—C5—H5D	56.3	C114—C115—H115	120
H5C—C5—H5D	56.3	C116—C115—H115	120
C4—C5—H5E	109.5	C115—C116—C111	120.08 (17)
H5A—C5—H5E	56.3	C115—C116—H116	120
H5B—C5—H5E	141.1	C111—C116—H116	120
H5C—C5—H5E	56.3	C2—N11—C111	128.22 (16)
H5D—C5—H5E	109.5	C2—N11—H11	115.9
C4—C5—H5F	109.5	C111—N11—H11	115.9
H5A—C5—H5F	56.3
N11—C2—C3—C4	1.9 (3)	C112—C113—C114—C115	−0.1 (3)
C1—C2—C3—C4	−178.62 (17)	C113—C114—C115—C116	1.1 (3)
C2—C3—C4—O12	−2.6 (3)	C114—C115—C116—C111	−1.4 (3)
C2—C3—C4—C5	177.01 (17)	C112—C111—C116—C115	0.7 (3)
C116—C111—C112—C113	0.3 (3)	N11—C111—C116—C115	177.51 (16)
N11—C111—C112—C113	−176.63 (16)	C3—C2—N11—C111	−177.32 (17)
C116—C111—C112—C12	−179.96 (16)	C1—C2—N11—C111	3.2 (3)
N11—C111—C112—C12	3.1 (3)	C116—C111—N11—C2	48.9 (3)
C111—C112—C113—C114	−0.6 (3)	C112—C111—N11—C2	−134.19 (19)
C12—C112—C113—C114	179.64 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O12	0.91	1.90	2.6345 (19)	136

Parameters	(I)	(II)	(III)	(IV)
N11—C111	1.422 (2)	1.521 (4)/1.463 (3)	1.440 (4)	-
N11—C2	1.345 (2)	1.320 (4)	1.319 (4)	1.303 (6)
O12—C4	1.257 (2)	1.290 (3)	1.291 (4)	1.281 (6)
C2—C3	1.383 (3)	1.410 (4)	1.423 (4)	1.396 (7)
C3—C4	1.420 (2)	1.365 (3)	1.382 (3)	1.388 (9)
N11···O12	2.635 (2)	2.885 (3)	2.886 (3)	2.826 (6)
N11—C2—C4—O12	-0.5 (1)	4.1 (2)	-2.6 (2)	1.2 (4)
Dihedral angle	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
N11—H11⋯O12	0.91	1.90	2.6345 (19)	136

Table 2

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

Parameters	(I)	(II)	(III)	(IV)
C111—N11	1.422 (2)	1.521 (4)/1.463 (3)	1.440 (4)	-
C2—N11	1.345 (2)	1.320 (4)	1.319 (4)	1.303 (6)
C4—O12	1.257 (2)	1.290 (3)	1.291 (4)	1.281 (6)
C2—C3	1.383 (3)	1.410 (4)	1.423 (4)	1.396 (7)
C3—C4	1.420 (2)	1.365 (3)	1.382 (3)	1.388 (9)
O12⋯N11	2.635 (2)	2.885 (3)	2.886 (3)	2.826 (6)
N11—C2—C4—O12	−0.5 (1)	4.1 (2)	−2.6 (2)	1.2 (4)
Dihedral angle	49.53 (5)	87.47 (4)/89.36 (8)	85.58 (8)	-

Notes: (I) This work; (II) N,O-bid = 4-(2,3-dimethyl phenyl­amino)­pent-3-en-2-onato (Venter et al., 2009a ▶); (III) N,O-bid = 4-(2,6-dimethyl phenyl­amino)­pent-3-en-2-onato (Venter et al., 2009b ▶). (IV) N,O-bid = 4-amino-pent-3-en-2-onato (Damoense et al., 1994 ▶). The dihedral angle is defined as the torsion angle between the N–C–C–C–O plane and the benzene ring. A positive angle denotes a clockwise rotation.