(E)-3-Dimethyl­amino-1-(1,3-thia­zol-2-yl)prop-2-en-1-one

You, X.-Y.; Shi, Y.-J.; Yu, L.-T.

doi:10.1107/S1600536812048817

organic compounds

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Volume 69| Part 1| January 2013| Page o18

https://doi.org/10.1107/S1600536812048817

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(E)-3-Dimethylamino-1-(1,3-thiazol-2-yl)prop-2-en-1-one

Xin-Yu You,^a Yao-Jie Shi ^b and Luo-Ting Yu ^b ^*

^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

(Received 19 November 2012; accepted 28 November 2012; online 5 December 2012)

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.

Related literature

For the biological activity of enaminone derivatives, see: Zeng (2010 ).

Experimental

Crystal data

C₈H₁₀N₂OS
M_r = 182.24
Monoclinic, P 2₁ /n
a = 5.6252 (2) Å
b = 22.5957 (8) Å
c = 7.5777 (3) Å
β = 109.498 (4)°
V = 907.93 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 135 K
0.35 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.974, T_max = 1.000
3683 measured reflections
1846 independent reflections
1565 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.06
1846 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯Cg1^iv	0.98	2.93	3.549 (2)	122
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z; (iii) x+1, y, z; (iv) x, y, z-1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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: OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812048817/vm2183sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

For the biological activity of enaminone derivatives, see: Zeng et al. (2010).

Experimental top

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.

Structure description top

For the biological activity of enaminone derivatives, see: Zeng et al. (2010).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: 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).

Figures top

	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.

(E)-3-Dimethylamino-1-(1,3-thiazol-2-yl)prop-2-en-1-one top

Crystal data top

C₈H₁₀N₂OS	F(000) = 384
M_r = 182.24	D_x = 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

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1846 independent reflections
Radiation source: Enhanced (Mo) X-ray Source	1565 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.0°
ω scans	h = −4→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	k = −13→28
T_min = 0.974, T_max = 1.000	l = −9→8
3683 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0388P)² + 0.2132P] where P = (F_o² + 2F_c²)/3
1846 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₈H₁₀N₂OS	V = 907.93 (6) Å³
M_r = 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)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1846 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	1565 reflections with I > 2σ(I)
T_min = 0.974, T_max = 1.000	R_int = 0.018
3683 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.06	Δρ_max = 0.28 e Å⁻³
1846 reflections	Δρ_min = −0.26 e Å⁻³
111 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg1^iv	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
M_r	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)
T_min, T_max	0.974, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3683, 1846, 1565
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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···Cg1^iv	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
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeng, X. X. (2010). Bioorg. Med. Chem. Lett. 20, 6282–6285. Web of Science CrossRef CAS PubMed Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page o18

https://doi.org/10.1107/S1600536812048817

Open

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