(2E)-3-(Dimethyl­amino)-1-(4-fluoro­phen­yl)prop-2-en-1-one

Kant, R.; Gupta, V.K.; Kapoor, K.; Deshmukh, M.B.; Patil, D.R.; Anbhule, P.V.

doi:10.1107/S160053681204202X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3110

doi:10.1107/S160053681204202X

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(2E)-3-(Dimethylamino)-1-(4-fluorophenyl)prop-2-en-1-one

Rajni Kant,^a ^* Vivek K. Gupta,^a Kamini Kapoor,^a Madhukar B. Deshmukh,^b D. R. Patil ^b and P. V. Anbhule ^b

^aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bDepartment of Chemistry, Shivaji University, Kolhapur 416 004, India
^*Correspondence e-mail: rkvk.paper11@gmail.com

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

In the title compound, C₁₁H₁₂FNO, the dihedral angle between the prop-2-en-1-one group and the benzene ring is 19.33 (6)°. The configuration of the keto group with respect to the olefinic double bond is s-cis. In the crystal, the molecules form dimers through aromatic π–π stacking interactions [centroid–centroid distance = 3.667 (1) Å] and are linked via C—H⋯O interactions into chains along the b axis.

Related literature

For the synthesis and pharmaceutical activity of enaminones, see: Kantevari et al. (2007 ); Ke et al. (2009 ); Omran et al. (1997 ); Eddington et al. (2003 ). For a related structure, see: Deng et al. (2010 ).

Experimental

Crystal data

C₁₁H₁₂FNO
M_r = 193.22
Monoclinic, P 2₁ /c
a = 13.2832 (6) Å
b = 5.8530 (2) Å
c = 14.2995 (8) Å
β = 116.086 (6)°
V = 998.49 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.824, T_max = 1.000
14183 measured reflections
1952 independent reflections
1430 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.133
S = 1.04
1952 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6B⋯O1ⁱ	0.96	2.59	3.531 (3)	168
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053681204202X/gk2520sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681204202X/gk2520Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681204202X/gk2520Isup3.cml

checkCIF report

Comment top

(2E)-3-(Dimethylamino)-1-(4-fluorophenyl)prop-2-en-1-one is a versatile substrate used for synthesis of number of heterocyclic compounds and drug intermediates (Kantevari et al., 2007; Ke et al., 2009; Omran et al., 1997; Eddington et al., 2003).

The molecular structure of the title compound (I) is shown in Fig.1. The bond lengths and angles observed in (I) show normal values and are comparable with a related structure (Deng et al., 2010). The dihedral angle between prop-2-en-1-one group and the phenyl ring is 19.33 (6) °. Molecules in the unit cell are packed together to form one dimensional assembly along the b axis (Fig.2) through intermolecular C6—H6B···O1 interactions (Table 1). The crystal structure is further stabilized by π–π interactions between the benzene ring (C7—C12) of the molecule at (x, y, z) and the benzene ring of an inversion related molecule at (- x, - y, -z)[centroid separation = 3.667 (1) Å, interplanar spacing = 3.535 Å and centroid shift = 0.97 Å].

Related literature top

For the synthesis and pharmaceutical activity of enaminones, see: Kantevari et al. (2007); Ke et al. (2009); Omran et al. (1997); Eddington et al. (2003). For a related structure, see: Deng et al. (2010).

Experimental top

In a 50 ml round bottom flask charged with 5 mmole of 4-methyl acetophenone and 5 mmole of dimethylformamide dimethyl acetal. Then 10 ml toulene was added and the reaction mixture was stirred for 3 h at 110°C. The reaction was monitored by TLC. After completion of reaction and cooling the reaction mixture was evaporated under vacuum. Finally, the product was isolated by column chromatography using ethyl acetate and n-hexane(2/8 vol.). Yield: 85%. IR(KBr): 1643, 1598, 1550,1439 cm-1. ¹H NMR (300 MHz, CDCl3): 2.93(s, 3H, N—CH3), 3.15(s, 3H, N—CH3), 5.65–5.69 (d, 1H, =CH), 7.79–7.83(d, 1H,=CH), 7.05–7.11(m, 2H, Ar—H), 7.89–7.94 (m, 2H, Ar—H).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing arrangement of molecules viewed down the a axis. The broken lines show the intermolecular C—H···O interactions.

(2E)-3-(Dimethylamino)-1-(4-fluorophenyl)prop-2-en-1-one top

Crystal data top

C₁₁H₁₂FNO	F(000) = 408
M_r = 193.22	D_x = 1.285 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 336–335 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.2832 (6) Å	Cell parameters from 5766 reflections
b = 5.8530 (2) Å	θ = 3.5–29.0°
c = 14.2995 (8) Å	µ = 0.10 mm⁻¹
β = 116.086 (6)°	T = 293 K
V = 998.49 (8) Å³	Block, yellow
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1952 independent reflections
Radiation source: fine-focus sealed tube	1430 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scan	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −7→7
T_min = 0.824, T_max = 1.000	l = −17→17
14183 measured reflections

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0668P)² + 0.1767P] where P = (F_o² + 2F_c²)/3
1952 reflections	(Δ/σ)_max = 0.002
129 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₁H₁₂FNO	V = 998.49 (8) Å³
M_r = 193.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2832 (6) Å	µ = 0.10 mm⁻¹
b = 5.8530 (2) Å	T = 293 K
c = 14.2995 (8) Å	0.3 × 0.2 × 0.2 mm
β = 116.086 (6)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1952 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1430 reflections with I > 2σ(I)
T_min = 0.824, T_max = 1.000	R_int = 0.040
14183 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
1952 reflections	Δρ_min = −0.16 e Å⁻³
129 parameters

Special details top

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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 > σ(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
C7	0.14077 (14)	0.3879 (3)	0.44568 (12)	0.0387 (4)
F1	−0.19144 (9)	0.5459 (2)	0.27506 (10)	0.0802 (4)
O1	0.28148 (11)	0.1122 (2)	0.52645 (12)	0.0752 (5)
C1	0.26094 (15)	0.3183 (3)	0.50936 (13)	0.0463 (4)
C2	0.34503 (14)	0.4916 (3)	0.54818 (13)	0.0457 (4)
H2	0.3259	0.6447	0.5332	0.055*
C3	0.45299 (14)	0.4299 (3)	0.60714 (13)	0.0489 (5)
H3	0.4653	0.2738	0.6186	0.059*
N4	0.54383 (12)	0.5600 (2)	0.65100 (12)	0.0548 (5)
C5	0.53933 (17)	0.8047 (3)	0.63606 (18)	0.0656 (6)
H5A	0.5800	0.8453	0.5972	0.098*
H5B	0.5724	0.8793	0.7026	0.098*
H5C	0.4627	0.8520	0.5985	0.098*
C6	0.65389 (16)	0.4629 (4)	0.71403 (17)	0.0689 (6)
H6A	0.6486	0.2993	0.7130	0.103*
H6B	0.6810	0.5165	0.7844	0.103*
H6C	0.7048	0.5088	0.6863	0.103*
C8	0.05728 (15)	0.2340 (3)	0.43627 (13)	0.0460 (4)
H8	0.0773	0.0921	0.4684	0.055*
C9	−0.05434 (15)	0.2869 (3)	0.38041 (14)	0.0510 (5)
H9	−0.1098	0.1845	0.3761	0.061*
C10	−0.08165 (14)	0.4935 (3)	0.33139 (13)	0.0476 (5)
C11	−0.00276 (15)	0.6494 (3)	0.33688 (13)	0.0468 (5)
H11	−0.0240	0.7880	0.3018	0.056*
C12	0.10921 (14)	0.5974 (3)	0.39551 (13)	0.0424 (4)
H12	0.1638	0.7035	0.4014	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0408 (9)	0.0342 (8)	0.0392 (8)	−0.0007 (7)	0.0158 (7)	−0.0018 (7)
F1	0.0383 (7)	0.0777 (9)	0.1045 (10)	0.0076 (6)	0.0130 (7)	0.0085 (7)
O1	0.0530 (9)	0.0379 (7)	0.1041 (12)	0.0033 (6)	0.0066 (8)	0.0109 (7)
C1	0.0446 (10)	0.0361 (9)	0.0504 (10)	0.0021 (7)	0.0136 (8)	0.0031 (7)
C2	0.0405 (10)	0.0367 (9)	0.0522 (10)	0.0028 (7)	0.0134 (8)	0.0008 (7)
C3	0.0454 (11)	0.0380 (9)	0.0542 (10)	0.0017 (8)	0.0134 (8)	−0.0009 (8)
N4	0.0370 (8)	0.0433 (9)	0.0680 (10)	0.0025 (7)	0.0082 (7)	−0.0015 (7)
C5	0.0526 (12)	0.0458 (11)	0.0848 (15)	−0.0024 (9)	0.0179 (11)	−0.0022 (10)
C6	0.0416 (11)	0.0642 (13)	0.0804 (14)	0.0076 (10)	0.0080 (10)	0.0013 (11)
C8	0.0483 (10)	0.0364 (9)	0.0476 (10)	−0.0037 (7)	0.0159 (8)	0.0032 (7)
C9	0.0436 (10)	0.0489 (10)	0.0585 (11)	−0.0102 (8)	0.0206 (9)	−0.0012 (8)
C10	0.0363 (9)	0.0504 (10)	0.0501 (10)	0.0031 (8)	0.0134 (8)	−0.0041 (8)
C11	0.0483 (10)	0.0382 (9)	0.0496 (10)	0.0068 (8)	0.0175 (8)	0.0034 (7)
C12	0.0410 (9)	0.0368 (9)	0.0487 (9)	−0.0023 (7)	0.0191 (8)	0.0013 (7)

Geometric parameters (Å, º) top

C7—C8	1.389 (2)	C5—H5B	0.9600
C7—C12	1.389 (2)	C5—H5C	0.9600
C7—C1	1.505 (2)	C6—H6A	0.9600
F1—C10	1.355 (2)	C6—H6B	0.9600
O1—C1	1.237 (2)	C6—H6C	0.9600
C1—C2	1.428 (2)	C8—C9	1.375 (2)
C2—C3	1.354 (2)	C8—H8	0.9300
C2—H2	0.9300	C9—C10	1.365 (3)
C3—N4	1.328 (2)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.365 (3)
N4—C5	1.445 (2)	C11—C12	1.382 (2)
N4—C6	1.454 (2)	C11—H11	0.9300
C5—H5A	0.9600	C12—H12	0.9300

C8—C7—C12	118.41 (16)	N4—C6—H6A	109.5
C8—C7—C1	118.20 (15)	N4—C6—H6B	109.5
C12—C7—C1	123.39 (16)	H6A—C6—H6B	109.5
O1—C1—C2	123.30 (16)	N4—C6—H6C	109.5
O1—C1—C7	117.81 (16)	H6A—C6—H6C	109.5
C2—C1—C7	118.89 (14)	H6B—C6—H6C	109.5
C3—C2—C1	119.05 (16)	C9—C8—C7	121.44 (16)
C3—C2—H2	120.5	C9—C8—H8	119.3
C1—C2—H2	120.5	C7—C8—H8	119.3
N4—C3—C2	129.38 (17)	C10—C9—C8	118.23 (17)
N4—C3—H3	115.3	C10—C9—H9	120.9
C2—C3—H3	115.3	C8—C9—H9	120.9
C3—N4—C5	121.90 (15)	F1—C10—C9	118.63 (16)
C3—N4—C6	121.72 (16)	F1—C10—C11	118.78 (16)
C5—N4—C6	116.35 (16)	C9—C10—C11	122.59 (16)
N4—C5—H5A	109.5	C10—C11—C12	118.80 (16)
N4—C5—H5B	109.5	C10—C11—H11	120.6
H5A—C5—H5B	109.5	C12—C11—H11	120.6
N4—C5—H5C	109.5	C11—C12—C7	120.49 (16)
H5A—C5—H5C	109.5	C11—C12—H12	119.8
H5B—C5—H5C	109.5	C7—C12—H12	119.8

C8—C7—C1—O1	19.2 (3)	C1—C7—C8—C9	179.18 (16)
C12—C7—C1—O1	−160.52 (17)	C7—C8—C9—C10	1.8 (3)
C8—C7—C1—C2	−159.98 (17)	C8—C9—C10—F1	179.16 (15)
C12—C7—C1—C2	20.4 (3)	C8—C9—C10—C11	−0.8 (3)
O1—C1—C2—C3	−0.3 (3)	F1—C10—C11—C12	179.12 (15)
C7—C1—C2—C3	178.80 (16)	C9—C10—C11—C12	−0.9 (3)
C1—C2—C3—N4	−179.93 (18)	C10—C11—C12—C7	1.6 (3)
C2—C3—N4—C5	−3.2 (3)	C8—C7—C12—C11	−0.6 (3)
C2—C3—N4—C6	178.8 (2)	C1—C7—C12—C11	179.03 (15)
C12—C7—C8—C9	−1.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O1ⁱ	0.96	2.59	3.531 (3)	168

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂FNO
M_r	193.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.2832 (6), 5.8530 (2), 14.2995 (8)
β (°)	116.086 (6)
V (Å³)	998.49 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.824, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14183, 1952, 1430
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.133, 1.04
No. of reflections	1952
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.16

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O1ⁱ	0.96	2.59	3.531 (3)	168

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. He is also thankful to the University of Jammu, Jammu, India, for financial support.

References

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