organic compounds
(E)-3-Dimethylamino-1-(1,3-thiazol-2-yl)prop-2-en-1-one
aDepartment of Pharmaceutical and Bioengineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China, and bState Key Laboratory of Biotherapy and Cancer Center, West China Hospital, West China Medical School, Sichuan University, Chengdu 610041, People's Republic of China
*Correspondence e-mail: yuluot@scu.edu.cn
In the title compound, C8H10N2OS, the 3-(dimethylamino)prop-2-en-1-one unit is approximately planar [give r.m.s. deviation] and the mean plane through the seven non-H atoms makes a dihedral angle of 8.88 (3)° with the thiazole ring. The carbonyl and ring C=N double bonds adjacent to the carbonyl group are trans [N—C—C—O = 172.31 (15) °], while the conformation of the carbonyl and propene double bonds is cis [O—C—C—C = 2.2 (2)°]. In the crystal, short C—H⋯N and C—H⋯O interactions together with C—H⋯π interactions generate a three-dimensional network.
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2006); 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: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2.
Supporting information
https://doi.org/10.1107/S1600536812048817/vm2183sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048817/vm2183Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812048817/vm2183Isup3.cml
A solution of 6.36 g (50.0 mmol) of 1-thiazol-2-yl-ethanone in 16.03 ml (17.87 g,150.0 mmol) of DMF-DMA (dimethoxy-N,N-dimethylmethanamine) was stirred for 24 h at 114°C. The solvent was evaporated and the title compound was recrystallized from ethanol. Yield: 6.83 g (75%). Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of ethyl acetate.
All H atoms were positioned geometrically (for methyl, C—H = 0.98 Å; for the other H atoms, C—H = 0.95 Å) and refined using a riding model, withUiso(H) = kUeq(C), where k = 1.5 for methyl and 1.2 for all other H atoms.
Enaminone derivatives are of great importance in organic synthesis (Zeng et al., 2010). The title compound is one of the key intermediates in our synthetic investigations on compounds active against of anti-hepatocellular carcinoma and cancers. We report here its crystal structure.
In the title compound, C8H10N2OS, (Fig.1), the dihedral angle between the thiazole ring and the mean plane through the remaining non-hydrogen atoms [O1/C4 - C9] is 8.88 (3) °. The two double bonds C1═N1 and C4═O1 are in trans (N1—C1—C4—O1: 172.31 (15) °), and the C4═O1 and C5═C6 double bonds are in cis (O1—C4—C5—C6: 2.2 (2) °).
In the crystal packing (Fig.2), the molecules are stabilized by short intermolecular C—H···N/O interactions and a C9—H9···Cg1 interaction (Cg1 is the centroid of the S1/N1/C1-C3 ring, Table 1).
For the biological activity of enaminone derivatives, see: Zeng et al. (2010).
Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell
CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. | |
Fig. 2. A crystal packing diagram of the title compound. The dashed lines represent C—H···π interactions. |
C8H10N2OS | F(000) = 384 |
Mr = 182.24 | Dx = 1.333 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
a = 5.6252 (2) Å | Cell parameters from 1788 reflections |
b = 22.5957 (8) Å | θ = 3.0–28.8° |
c = 7.5777 (3) Å | µ = 0.31 mm−1 |
β = 109.498 (4)° | T = 135 K |
V = 907.93 (6) Å3 | Block, yellow |
Z = 4 | 0.35 × 0.30 × 0.30 mm |
Oxford Diffraction Xcalibur Eos diffractometer | 1846 independent reflections |
Radiation source: Enhanced (Mo) X-ray Source | 1565 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 16.0874 pixels mm-1 | θmax = 26.4°, θmin = 3.0° |
ω scans | h = −4→7 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006) | k = −13→28 |
Tmin = 0.974, Tmax = 1.000 | l = −9→8 |
3683 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0388P)2 + 0.2132P] where P = (Fo2 + 2Fc2)/3 |
1846 reflections | (Δ/σ)max < 0.001 |
111 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C8H10N2OS | V = 907.93 (6) Å3 |
Mr = 182.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.6252 (2) Å | µ = 0.31 mm−1 |
b = 22.5957 (8) Å | T = 135 K |
c = 7.5777 (3) Å | 0.35 × 0.30 × 0.30 mm |
β = 109.498 (4)° |
Oxford Diffraction Xcalibur Eos diffractometer | 1846 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006) | 1565 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 1.000 | Rint = 0.018 |
3683 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.28 e Å−3 |
1846 reflections | Δρmin = −0.26 e Å−3 |
111 parameters |
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.19, 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 | ||
S1 | 0.48299 (8) | 0.15794 (2) | 0.44117 (6) | 0.02965 (16) | |
O1 | 0.5387 (2) | 0.06419 (5) | 0.19443 (16) | 0.0293 (3) | |
N1 | 0.8366 (2) | 0.20354 (6) | 0.34119 (19) | 0.0269 (3) | |
N2 | 0.9036 (2) | 0.06400 (6) | −0.19641 (18) | 0.0243 (3) | |
C1 | 0.6877 (3) | 0.15752 (7) | 0.3145 (2) | 0.0214 (4) | |
C2 | 0.6091 (3) | 0.22388 (9) | 0.5379 (2) | 0.0347 (4) | |
H2 | 0.5586 | 0.2455 | 0.6269 | 0.042* | |
C3 | 0.7920 (3) | 0.24077 (8) | 0.4690 (2) | 0.0336 (4) | |
H3 | 0.8841 | 0.2765 | 0.5073 | 0.040* | |
C4 | 0.6732 (3) | 0.10684 (7) | 0.1844 (2) | 0.0215 (4) | |
C5 | 0.8103 (3) | 0.11210 (7) | 0.0581 (2) | 0.0226 (4) | |
H5 | 0.9141 | 0.1456 | 0.0619 | 0.027* | |
C6 | 0.7890 (3) | 0.06752 (7) | −0.0696 (2) | 0.0221 (4) | |
H6 | 0.6800 | 0.0357 | −0.0667 | 0.026* | |
C8 | 0.8565 (3) | 0.01509 (8) | −0.3283 (2) | 0.0308 (4) | |
H8A | 0.7469 | −0.0140 | −0.2980 | 0.046* | |
H8B | 1.0169 | −0.0037 | −0.3203 | 0.046* | |
H8C | 0.7740 | 0.0300 | −0.4556 | 0.046* | |
C9 | 1.0815 (3) | 0.10914 (9) | −0.2102 (2) | 0.0342 (4) | |
H9A | 1.0028 | 0.1482 | −0.2203 | 0.051* | |
H9B | 1.1291 | 0.1017 | −0.3214 | 0.051* | |
H9C | 1.2324 | 0.1078 | −0.0982 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0328 (3) | 0.0320 (3) | 0.0283 (3) | 0.00526 (19) | 0.0159 (2) | −0.00177 (19) |
O1 | 0.0389 (7) | 0.0259 (7) | 0.0287 (6) | −0.0064 (6) | 0.0186 (5) | −0.0032 (5) |
N1 | 0.0274 (7) | 0.0248 (8) | 0.0253 (7) | 0.0021 (6) | 0.0046 (6) | −0.0015 (6) |
N2 | 0.0267 (7) | 0.0290 (8) | 0.0204 (7) | 0.0021 (6) | 0.0121 (6) | 0.0029 (6) |
C1 | 0.0214 (8) | 0.0238 (9) | 0.0178 (8) | 0.0062 (7) | 0.0050 (6) | 0.0029 (7) |
C2 | 0.0428 (10) | 0.0309 (10) | 0.0292 (9) | 0.0115 (9) | 0.0102 (8) | −0.0059 (8) |
C3 | 0.0378 (10) | 0.0255 (10) | 0.0318 (9) | 0.0040 (8) | 0.0040 (8) | −0.0064 (8) |
C4 | 0.0232 (8) | 0.0223 (8) | 0.0179 (8) | 0.0028 (7) | 0.0052 (6) | 0.0026 (7) |
C5 | 0.0238 (8) | 0.0235 (9) | 0.0209 (8) | −0.0005 (7) | 0.0079 (7) | 0.0018 (7) |
C6 | 0.0225 (8) | 0.0253 (9) | 0.0190 (8) | 0.0021 (7) | 0.0077 (6) | 0.0055 (7) |
C8 | 0.0439 (10) | 0.0298 (10) | 0.0247 (9) | 0.0073 (8) | 0.0193 (8) | 0.0019 (8) |
C9 | 0.0297 (9) | 0.0466 (12) | 0.0299 (9) | −0.0064 (9) | 0.0148 (8) | 0.0032 (9) |
S1—C1 | 1.7282 (16) | C3—H3 | 0.9500 |
S1—C2 | 1.707 (2) | C4—C5 | 1.420 (2) |
O1—C4 | 1.2432 (19) | C5—H5 | 0.9500 |
N1—C1 | 1.308 (2) | C5—C6 | 1.374 (2) |
N1—C3 | 1.368 (2) | C6—H6 | 0.9500 |
N2—C6 | 1.3264 (19) | C8—H8A | 0.9800 |
N2—C8 | 1.454 (2) | C8—H8B | 0.9800 |
N2—C9 | 1.457 (2) | C8—H8C | 0.9800 |
C1—C4 | 1.495 (2) | C9—H9A | 0.9800 |
C2—H2 | 0.9500 | C9—H9B | 0.9800 |
C2—C3 | 1.355 (3) | C9—H9C | 0.9800 |
C2—S1—C1 | 89.13 (9) | C6—C5—C4 | 118.28 (15) |
C1—N1—C3 | 109.85 (14) | C6—C5—H5 | 120.9 |
C6—N2—C8 | 121.51 (14) | N2—C6—C5 | 127.23 (16) |
C6—N2—C9 | 121.45 (15) | N2—C6—H6 | 116.4 |
C8—N2—C9 | 117.04 (13) | C5—C6—H6 | 116.4 |
N1—C1—S1 | 114.87 (12) | N2—C8—H8A | 109.5 |
N1—C1—C4 | 127.05 (14) | N2—C8—H8B | 109.5 |
C4—C1—S1 | 118.07 (12) | N2—C8—H8C | 109.5 |
S1—C2—H2 | 125.0 | H8A—C8—H8B | 109.5 |
C3—C2—S1 | 109.92 (14) | H8A—C8—H8C | 109.5 |
C3—C2—H2 | 125.0 | H8B—C8—H8C | 109.5 |
N1—C3—H3 | 121.9 | N2—C9—H9A | 109.5 |
C2—C3—N1 | 116.23 (17) | N2—C9—H9B | 109.5 |
C2—C3—H3 | 121.9 | N2—C9—H9C | 109.5 |
O1—C4—C1 | 116.99 (14) | H9A—C9—H9B | 109.5 |
O1—C4—C5 | 125.77 (15) | H9A—C9—H9C | 109.5 |
C5—C4—C1 | 117.22 (14) | H9B—C9—H9C | 109.5 |
C4—C5—H5 | 120.9 | ||
S1—C1—C4—O1 | −9.54 (19) | C1—C4—C5—C6 | −176.53 (13) |
S1—C1—C4—C5 | 169.33 (11) | C2—S1—C1—N1 | −0.70 (13) |
S1—C2—C3—N1 | 0.2 (2) | C2—S1—C1—C4 | −179.08 (13) |
O1—C4—C5—C6 | 2.2 (2) | C3—N1—C1—S1 | 0.92 (17) |
N1—C1—C4—O1 | 172.31 (15) | C3—N1—C1—C4 | 179.13 (15) |
N1—C1—C4—C5 | −8.8 (2) | C4—C5—C6—N2 | −179.08 (15) |
C1—S1—C2—C3 | 0.25 (14) | C8—N2—C6—C5 | −177.66 (15) |
C1—N1—C3—C2 | −0.7 (2) | C9—N2—C6—C5 | 2.1 (3) |
Cg1 is the centroid of the S1/N1/C1–C3 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N1i | 0.95 | 2.62 | 3.560 (2) | 169 |
C6—H6···O1ii | 0.95 | 2.60 | 3.462 (2) | 151 |
C8—H8A···O1ii | 0.98 | 2.31 | 3.269 (2) | 167 |
C9—H9C···O1iii | 0.98 | 2.51 | 3.433 (2) | 157 |
C9—H9A···Cg1iv | 0.98 | 2.93 | 3.549 (2) | 122 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z; (iii) x+1, y, z; (iv) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C8H10N2OS |
Mr | 182.24 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 135 |
a, b, c (Å) | 5.6252 (2), 22.5957 (8), 7.5777 (3) |
β (°) | 109.498 (4) |
V (Å3) | 907.93 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.35 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Eos |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.974, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3683, 1846, 1565 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.090, 1.06 |
No. of reflections | 1846 |
No. of parameters | 111 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.26 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006), OLEX2 (Dolomanov et al., 2009).
Cg1 is the centroid of the S1/N1/C1–C3 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N1i | 0.95 | 2.62 | 3.560 (2) | 169.3 |
C6—H6···O1ii | 0.95 | 2.60 | 3.462 (2) | 151.4 |
C8—H8A···O1ii | 0.98 | 2.31 | 3.269 (2) | 166.8 |
C9—H9C···O1iii | 0.98 | 2.51 | 3.433 (2) | 156.5 |
C9—H9A···Cg1iv | 0.98 | 2.93 | 3.549 (2) | 122.0 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z; (iii) x+1, y, z; (iv) x, y, z−1. |
Acknowledgements
We thank the Analytical and Testing Center of Sichuan University for the X-ray data collection.
References
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Enaminone derivatives are of great importance in organic synthesis (Zeng et al., 2010). The title compound is one of the key intermediates in our synthetic investigations on compounds active against of anti-hepatocellular carcinoma and cancers. We report here its crystal structure.
In the title compound, C8H10N2OS, (Fig.1), the dihedral angle between the thiazole ring and the mean plane through the remaining non-hydrogen atoms [O1/C4 - C9] is 8.88 (3) °. The two double bonds C1═N1 and C4═O1 are in trans (N1—C1—C4—O1: 172.31 (15) °), and the C4═O1 and C5═C6 double bonds are in cis (O1—C4—C5—C6: 2.2 (2) °).
In the crystal packing (Fig.2), the molecules are stabilized by short intermolecular C—H···N/O interactions and a C9—H9···Cg1 interaction (Cg1 is the centroid of the S1/N1/C1-C3 ring, Table 1).