organic compounds
(2E)-3-(Dimethylamino)-1-(4-fluorophenyl)prop-2-en-1-one
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
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
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell 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
10.1107/S160053681204202X/gk2520sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204202X/gk2520Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681204202X/gk2520Isup3.cml
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
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).All H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93–0.96 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
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).C11H12FNO | F(000) = 408 |
Mr = 193.22 | Dx = 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 |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 1952 independent reflections |
Radiation source: fine-focus sealed tube | 1430 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 16.1049 pixels mm-1 | θmax = 26.0°, θmin = 3.5° |
ω scan | h = −16→16 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −7→7 |
Tmin = 0.824, Tmax = 1.000 | l = −17→17 |
14183 measured reflections |
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(Fo2) + (0.0668P)2 + 0.1767P] where P = (Fo2 + 2Fc2)/3 |
1952 reflections | (Δ/σ)max = 0.002 |
129 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C11H12FNO | V = 998.49 (8) Å3 |
Mr = 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)° |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 1952 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1430 reflections with I > 2σ(I) |
Tmin = 0.824, Tmax = 1.000 | Rint = 0.040 |
14183 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.20 e Å−3 |
1952 reflections | Δρmin = −0.16 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.824, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14183, 1952, 1430 |
Rint | 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 |
Δρmax, Δρmin (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).
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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(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].