4-(2-Chloro­phenyl­amino)-pent-3-en-2-one

Venter, G.J.S.; Brink, A.; Steyl, G.; Roodt, A.

doi:10.1107/S1600536812042043

organic compounds

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Volume 68| Part 11| November 2012| Pages o3101-o3102

doi:10.1107/S1600536812042043

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4-(2-Chlorophenylamino)-pent-3-en-2-one

Gertruida J.S. Venter,^a ^* Alice Brink,^a Gideon Steyl ^a and Andreas Roodt ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, 9300, South Africa
^*Correspondence e-mail: ventergjs@ufs.ac.za

(Received 21 September 2012; accepted 8 October 2012; online 13 October 2012)

In the title compound, C₁₁H₁₂ClNO, intramolecular N—H⋯O hydrogen bonding is present. The dihedral angle between the benzene ring and the pentenone unit is 46.52 (5)°. In the crystal, C—H⋯O interactions between hydrogen atoms of the aryl moiety and two separate oxygen atoms occur, leading to a three-dimensional network.

Related literature

For synthetic background and similar compounds, see: Shaheen et al. (2006 ); Venter et al. (2010 , 2012b ). For applications, see: Brink et al. (2010 ); Pyżuk et al. (1993 ); Roodt & Steyn (2000 ); Tan et al. (2008 ); Xia et al. (2008 ). For related ligand systems, see: Damoense et al. (1994 ), Venter et al. (2012a ).

Experimental

Crystal data

C₁₁H₁₂ClNO
M_r = 209.67
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.3264 (3) Å
b = 8.7103 (4) Å
c = 16.1960 (7) Å
V = 1033.55 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.6 × 0.42 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.825, T_max = 0.933
17399 measured reflections
2259 independent reflections
2211 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.068
S = 1.06
2259 reflections
126 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 932 Friedel pairs
Flack parameter: 0.01 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O12	0.82	1.95	2.6317 (16)	139
C113—H113⋯O12ⁱ	0.95	2.42	3.3536 (18)	166
C115—H115⋯O12ⁱⁱ	0.95	2.43	3.3217 (18)	157
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y+1, z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812042043/pk2444sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042043/pk2444Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812042043/pk2444Isup3.cml

checkCIF report

Comment top

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, contains both nitrogen and oxygen atoms with an unsaturated C═C bond, and is of interest in various fields including liquid crystals [Pyżuk et al. (1993)], fluorescence studies [Xia et al. (2008)], medicine [Tan et al. (2008)] and catalysis [Roodt & Steyn (2000); Brink et al. (2010)].

The title compound (Fig. 1) crystallizes in the orthorhombic space group P2₁2₁2₁ 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 [Venter et al. (2012a); Damoense et al. (1994)], but share characteristics with other enaminoketones of this type [Venter et al. (2010; 2012b). An unsaturated bond in the pentenone backbone is indicated by the difference in distance between the C₂═C₃ bond [1.379 (2) Å] and the C₃–C₄ bond [1.428 (2) Å]. The distance, N₁₁···O₁₂, is greatly increased (~ 0.2 Å) upon coordination. Intramolecular N₁₁—H₁₁···O₁₂ bonding (D—A distance = 2.632 (2) Å was observed, as well as intermolecular interactions for C₁₁₃—H₁₁₃···O₁₂i [i = x-0.5, 0.5-y, 1-z; distance = 3.3536 (18) Å] and C₁₁₅—H₁₁₅···O₁₂ii [ii = x, y+1, z; distance = 3.3217 (18) Å]. These interactions are illustrated in Fig. 2. The dihedral angle between the benzene ring and pentenone moieties is 46.52 (5)° and is dependent on the position of the substituent on the benzene ring, where para substituents usually display the smallest angles (Venter et al., 2010).

Related literature top

For synthetic background and similar compounds, see: Shaheen et al. (2006); Venter et al. (2010, 2012b). For applications, see: Brink et al. (2010); Pyżuk et al. (1993); Roodt & Steyn (2000); Tan et al. (2008); Xia et al. (2008). For related ligand systems, see: Damoense et al. (1994), Venter et al. (2012a).

Experimental top

A solution of acetylacetone (11.07 g, 0.1106 mol), 2-chloro-aniline (10.73 g, 0.1008 mol) and 2 drops of H₂SO₄ (conc.) in 150 ml benzene was refluxed for 6 h in a Dean-Stark trap, filtered and left to crystallize. Crystals suitable for X-ray diffraction were obtained in 17.86 g (94.32%) yield. This compound is stable in air and light over a period of several months.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. Partially filled unit cell illustrating the intra- and intermolecular hydrogen bonding interactions in the title compound, indicated with dashed lines.

4-(2-Chlorophenylamino)-pent-3-en-2-one top

Crystal data top

C₁₁H₁₂ClNO	F(000) = 440
M_r = 209.67	D_x = 1.347 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5717 reflections
a = 7.3264 (3) Å	θ = 2.7–28.3°
b = 8.7103 (4) Å	µ = 0.33 mm⁻¹
c = 16.1960 (7) Å	T = 100 K
V = 1033.55 (8) Å³	Cuboid, yellow
Z = 4	0.6 × 0.42 × 0.21 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2259 independent reflections
Radiation source: fine-focus sealed tube	2211 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→9
T_min = 0.825, T_max = 0.933	k = −11→11
17399 measured reflections	l = −20→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0376P)² + 0.2837P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.013
2259 reflections	Δρ_max = 0.21 e Å⁻³
126 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 932 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (5)

Crystal data top

C₁₁H₁₂ClNO	V = 1033.55 (8) Å³
M_r = 209.67	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.3264 (3) Å	µ = 0.33 mm⁻¹
b = 8.7103 (4) Å	T = 100 K
c = 16.1960 (7) Å	0.6 × 0.42 × 0.21 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2259 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2211 reflections with I > 2σ(I)
T_min = 0.825, T_max = 0.933	R_int = 0.032
17399 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	Δρ_max = 0.21 e Å⁻³
S = 1.06	Δρ_min = −0.24 e Å⁻³
2259 reflections	Absolute structure: Flack (1983), 932 Friedel pairs
126 parameters	Absolute structure parameter: 0.01 (5)
0 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
Cl12	0.00235 (5)	0.20519 (4)	0.531562 (19)	0.02339 (10)
N11	0.21805 (15)	0.28866 (14)	0.67897 (7)	0.0174 (2)
H11	0.2500 (8)	0.209 (2)	0.6556 (6)	0.027 (5)*
O12	0.33003 (14)	0.00171 (12)	0.68371 (6)	0.02136 (18)
C3	0.24678 (18)	0.14426 (16)	0.80149 (9)	0.0178 (3)
H3	0.2362	0.1411	0.8599	0.021*
C2	0.20915 (17)	0.28095 (16)	0.76209 (8)	0.0169 (3)
C111	0.18055 (18)	0.41335 (16)	0.62662 (8)	0.0166 (3)
C116	0.2464 (2)	0.56091 (16)	0.64159 (9)	0.0197 (3)
H116	0.3191	0.5797	0.6891	0.024*
C4	0.3006 (2)	0.00740 (18)	0.75983 (9)	0.02136 (18)
C113	0.04201 (19)	0.50725 (19)	0.49974 (9)	0.0229 (3)
H113	−0.0264	0.4881	0.451	0.027*
C5	0.3168 (2)	−0.13853 (17)	0.80936 (9)	0.0227 (3)
H5A	0.2032	−0.1974	0.8047	0.034*
H5B	0.339	−0.1131	0.8674	0.034*
H5C	0.4185	−0.2	0.7881	0.034*
C112	0.08035 (18)	0.38927 (17)	0.55421 (9)	0.0184 (3)
C115	0.20717 (19)	0.68074 (17)	0.58791 (9)	0.0226 (3)
H115	0.2505	0.7812	0.5996	0.027*
C1	0.1554 (2)	0.41966 (16)	0.81135 (9)	0.0203 (3)
H1A	0.2628	0.4845	0.8205	0.03*
H1B	0.1056	0.3871	0.8647	0.03*
H1C	0.0627	0.478	0.7811	0.03*
C114	0.1048 (2)	0.65395 (18)	0.51727 (9)	0.0243 (3)
H114	0.0776	0.7363	0.4808	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl12	0.02513 (17)	0.02720 (17)	0.01784 (17)	−0.00589 (15)	−0.00152 (14)	−0.00549 (12)
N11	0.0194 (5)	0.0181 (5)	0.0146 (5)	0.0016 (5)	−0.0004 (4)	−0.0024 (5)
O12	0.0232 (4)	0.0229 (4)	0.0180 (4)	−0.0007 (3)	0.0032 (3)	−0.0004 (3)
C3	0.0158 (6)	0.0234 (7)	0.0140 (7)	−0.0011 (5)	−0.0006 (5)	−0.0012 (5)
C2	0.0122 (6)	0.0218 (6)	0.0167 (6)	−0.0010 (5)	−0.0007 (5)	−0.0026 (5)
C111	0.0136 (6)	0.0216 (6)	0.0145 (6)	0.0013 (5)	0.0015 (5)	−0.0012 (5)
C116	0.0168 (6)	0.0224 (6)	0.0198 (7)	−0.0008 (5)	0.0010 (5)	−0.0028 (5)
C4	0.0232 (4)	0.0229 (4)	0.0180 (4)	−0.0007 (3)	0.0032 (3)	−0.0004 (3)
C113	0.0202 (7)	0.0333 (7)	0.0152 (6)	0.0025 (6)	0.0003 (5)	0.0019 (6)
C5	0.0211 (6)	0.0230 (7)	0.0241 (8)	0.0020 (6)	0.0011 (6)	0.0025 (6)
C112	0.0151 (6)	0.0236 (7)	0.0165 (7)	−0.0019 (5)	0.0026 (5)	−0.0027 (5)
C115	0.0212 (7)	0.0224 (7)	0.0242 (7)	−0.0013 (6)	0.0062 (5)	0.0008 (6)
C1	0.0212 (6)	0.0221 (7)	0.0175 (7)	0.0018 (5)	0.0007 (5)	−0.0032 (5)
C114	0.0228 (7)	0.0276 (7)	0.0224 (8)	0.0032 (6)	0.0042 (6)	0.0077 (6)

Geometric parameters (Å, º) top

Cl12—C112	1.7412 (15)	C4—C5	1.508 (2)
N11—C2	1.3494 (18)	C113—C112	1.383 (2)
N11—C111	1.4049 (18)	C113—C114	1.387 (2)
N11—H11	0.8243	C113—H113	0.95
O12—C4	1.2524 (18)	C5—H5A	0.98
C3—C2	1.3787 (19)	C5—H5B	0.98
C3—C4	1.425 (2)	C5—H5C	0.98
C3—H3	0.95	C115—C114	1.388 (2)
C2—C1	1.5005 (19)	C115—H115	0.95
C111—C116	1.3942 (19)	C1—H1A	0.98
C111—C112	1.3994 (19)	C1—H1B	0.98
C116—C115	1.389 (2)	C1—H1C	0.98
C116—H116	0.95	C114—H114	0.95

C2—N11—C111	129.12 (13)	C4—C5—H5A	109.5
C2—N11—H11	115.4	C4—C5—H5B	109.5
C111—N11—H11	115.4	H5A—C5—H5B	109.5
C2—C3—C4	123.95 (13)	C4—C5—H5C	109.5
C2—C3—H3	118	H5A—C5—H5C	109.5
C4—C3—H3	118	H5B—C5—H5C	109.5
N11—C2—C3	119.67 (12)	C113—C112—C111	121.98 (13)
N11—C2—C1	120.21 (13)	C113—C112—Cl12	118.89 (11)
C3—C2—C1	120.11 (12)	C111—C112—Cl12	119.13 (11)
C116—C111—C112	117.74 (13)	C114—C115—C116	120.12 (13)
C116—C111—N11	122.69 (12)	C114—C115—H115	119.9
C112—C111—N11	119.50 (12)	C116—C115—H115	119.9
C115—C116—C111	120.82 (13)	C2—C1—H1A	109.5
C115—C116—H116	119.6	C2—C1—H1B	109.5
C111—C116—H116	119.6	H1A—C1—H1B	109.5
O12—C4—C3	123.13 (14)	C2—C1—H1C	109.5
O12—C4—C5	118.48 (14)	H1A—C1—H1C	109.5
C3—C4—C5	118.35 (13)	H1B—C1—H1C	109.5
C112—C113—C114	119.11 (14)	C113—C114—C115	120.18 (14)
C112—C113—H113	120.4	C113—C114—H114	119.9
C114—C113—H113	120.4	C115—C114—H114	119.9

C111—N11—C2—C3	177.99 (12)	C114—C113—C112—C111	0.1 (2)
C111—N11—C2—C1	−0.9 (2)	C114—C113—C112—Cl12	−179.63 (11)
C4—C3—C2—N11	1.8 (2)	C116—C111—C112—C113	−1.8 (2)
C4—C3—C2—C1	−179.31 (13)	N11—C111—C112—C113	−178.91 (12)
C2—N11—C111—C116	46.2 (2)	C116—C111—C112—Cl12	177.84 (10)
C2—N11—C111—C112	−136.84 (15)	N11—C111—C112—Cl12	0.77 (17)
C112—C111—C116—C115	2.6 (2)	C111—C116—C115—C114	−1.5 (2)
N11—C111—C116—C115	179.53 (13)	C112—C113—C114—C115	1.1 (2)
C2—C3—C4—O12	4.7 (2)	C116—C115—C114—C113	−0.3 (2)
C2—C3—C4—C5	−173.14 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O12	0.82	1.95	2.6317 (16)	139
C113—H113···O12ⁱ	0.95	2.42	3.3536 (18)	166
C115—H115···O12ⁱⁱ	0.95	2.43	3.3217 (18)	157

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClNO
M_r	209.67
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.3264 (3), 8.7103 (4), 16.1960 (7)
V (Å³)	1033.55 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.6 × 0.42 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.825, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	17399, 2259, 2211
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.068, 1.06
No. of reflections	2259
No. of parameters	126
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24
Absolute structure	Flack (1983), 932 Friedel pairs
Absolute structure parameter	0.01 (5)

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O12	0.82	1.95	2.6317 (16)	139.2
C113—H113···O12ⁱ	0.95	2.42	3.3536 (18)	166.1
C115—H115···O12ⁱⁱ	0.95	2.43	3.3217 (18)	157.1

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

Acknowledgements

Financial assistance from the University of the Free State is gratefully acknowledged. We also express our gratitude towards SASOL, the South African National Research Foundation (SA-NRF/THRIP) and the Inkaba yeAfrica initiative 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.

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