2-(4-Chloro­phen­yl)-3-methyl-N-(5-methyl­thia­zol-2-yl)butanamide

Cheng, J.-L.; Zhao, J.-H.; Zhu, G.-N.; Lin, F.-C.

doi:10.1107/S1600536808043031

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o184

doi:10.1107/S1600536808043031

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2-(4-Chlorophenyl)-3-methyl-N-(5-methylthiazol-2-yl)butanamide

Jing-Li Cheng,^a Jin-Hao Zhao,^a Guo-Nian Zhu ^a and Fu-Cheng Lin ^b ^*

^aCollege of Agriculture and Biotechnology, Zhejiang University, Hangzhou 310029, People's Republic of China, and ^bInstitute of Biotechnology, Zhejiang University, Hangzhou 310029, People's Republic of China
^*Correspondence e-mail: fuchenglin@zj.com

(Received 19 November 2008; accepted 17 December 2008; online 20 December 2008)

In the title compound, C₁₅H₁₇ClN₂OS, the thiazole ring, which is essentially planar with a maximum deviation of 0.044 (3) Å, makes a dihedral angle of 54.76 (8)° with the benzene ring. In the crystal, adjacent molecules related by twofold rotation symmetry are linked by pairs of N—H⋯N hydrogen bonds.

Related literature

For background, see: Holmstead et al. (1978 ); Forlani (1978 ). For a related structure, see: Zhao et al. (2006 ).

Experimental

Crystal data

C₁₅H₁₇ClN₂OS
M_r = 308.83
Monoclinic, C 2/c
a = 14.9649 (6) Å
b = 17.6062 (7) Å
c = 12.5606 (5) Å
β = 99.9482 (11)°
V = 3259.6 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 298 (1) K
0.41 × 0.33 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.858, T_max = 0.911
15655 measured reflections
3708 independent reflections
2559 reflections with F² > 2σ(F²)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.172
S = 1.01
3708 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H111⋯N2ⁱ	0.86	2.08	2.929 (2)	168
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536808043031/is2368sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043031/is2368Isup2.hkl

checkCIF report

Comment top

2-(4-Chlorophenyl)-3-methylbutanoyl chloride is an intermediate in the synthesis of fenvalerate, an excellent insecticide (Holmstead et al., 1978). 2-Amino-5-methyl-thiazole is another heterocyclic intermediate (Forlani, 1978). As part of our continuing interest in the design and synthesis of new pesticides, we have isolated the title compound, (I), the product of the condensation reaction between 2-(4-chlorophenyl)-3-methylbutanoyl chloride and 5-methyl-2-aminothiazole, as colourless crystals suitable for X-ray analysis.

The molecular structure of (I) is illustrated in Fig. 1. Atoms N2, C10, C11, S1, C9 and N1 are coplanar, the largest deviation being 0.044 (3) Å for N1. As expected, the benzene ring is planar, and atom Cl1 lies only 0.018 (4) Å from the plane defined by the ring C atoms and itself. The angle between these two rings is 54.76 (8)°, smaller than the angle between the thiazole and benzene rings of the compound 2-(4-chlorophenyl)-3-methyl-N-(thiazol-2-yl) butanamide (Zhao et al., 2006). There are N—H···N interactions in the crystal structure, which lead to the formation of hydrogen-bonded dimers (Figs. 2 and 3).

Related literature top

For background, see: Holmstead et al. (1978); Forlani (1978). For a related structure, see: Zhao et al. (2006).

Experimental top

2-Amino-5-methylthiazole (1.14 g, 10 mmol), 4-dimethylaminopyridine (0.12 g), triethylamine (1.31 g) and chloroform (100 ml) were added to a 250 ml round flask. The mixture was stirred and cooled to 273 K, and then 2-(4-chlorophenyl)-3-methylbutanoyl chloride (3.47 g) was added dropwise within 30 min. The mixture was stirred at room temperature for 3 h and then 1% aqueous HCl was added (5 ml). The organic layer was washed with water to a neutral pH and dried over Na₂SO₄. After being filtered and concentrated, the organic residue was purified by silica-gel column chromatography, eluted with ethyl acetate-petroleum ether-formic acid (10:80:1, v/v/v), to give a white solid (yield 85%, 2.5 g), (I). It was then recrystallized from ethyl acetate-petroleum ether (2:1, v/v) to give colourless blocks (m.p. 460–461 K).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Molecular packing arrangement in the unit cell.
	Fig. 3. View showing the N—H···N hydrogen bonding (dashed lines) [symmetry code: (i) 1 - x, y, 3/2 - z].

2-(4-Chlorophenyl)-3-methyl-N-(5-methylthiazol-2-yl)butanamide top

Crystal data top

C₁₅H₁₇ClN₂OS	F(000) = 1296.00
M_r = 308.83	D_x = 1.258 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 10539 reflections
a = 14.9649 (6) Å	θ = 3.3–27.4°
b = 17.6062 (7) Å	µ = 0.36 mm⁻¹
c = 12.5606 (5) Å	T = 298 K
β = 99.9482 (11)°	Block, colorless
V = 3259.6 (2) Å³	0.41 × 0.33 × 0.26 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPID diffractometer	2559 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −19→19
T_min = 0.858, T_max = 0.911	k = −22→22
15655 measured reflections	l = −16→15
3708 independent reflections

Refinement top

Refinement on F²	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.121P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.172	(Δ/σ)_max = 0.001
S = 1.01	Δρ_max = 0.27 e Å⁻³
3708 reflections	Δρ_min = −0.29 e Å⁻³
183 parameters	Extinction correction: SHELXL
0 restraints	Extinction coefficient: 0.0028 (7)

Crystal data top

C₁₅H₁₇ClN₂OS	V = 3259.6 (2) Å³
M_r = 308.83	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.9649 (6) Å	µ = 0.36 mm⁻¹
b = 17.6062 (7) Å	T = 298 K
c = 12.5606 (5) Å	0.41 × 0.33 × 0.26 mm
β = 99.9482 (11)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3708 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2559 reflections with F² > 2σ(F²)
T_min = 0.858, T_max = 0.911	R_int = 0.027
15655 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.01	Δρ_max = 0.27 e Å⁻³
3708 reflections	Δρ_min = −0.29 e Å⁻³
183 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Cl1	0.02408 (6)	0.70387 (4)	0.59960 (9)	0.1206 (3)
S1	0.46203 (3)	0.39223 (3)	0.44117 (3)	0.0559 (2)
O1	0.29216 (10)	0.40983 (10)	0.48366 (10)	0.0696 (4)
N1	0.40090 (10)	0.41256 (9)	0.63283 (11)	0.0496 (3)
N2	0.55713 (11)	0.40575 (9)	0.63079 (12)	0.0530 (4)
C1	0.24241 (12)	0.41401 (12)	0.65622 (13)	0.0534 (4)
C2	0.18766 (12)	0.48677 (12)	0.64116 (13)	0.0531 (4)
C3	0.18371 (13)	0.53424 (12)	0.72811 (17)	0.0611 (5)
C4	0.13313 (17)	0.60024 (12)	0.7171 (2)	0.0739 (6)
C5	0.08679 (16)	0.61988 (13)	0.6158 (2)	0.0756 (6)
C6	0.08973 (17)	0.57396 (14)	0.5282 (2)	0.0790 (6)
C7	0.13902 (13)	0.50774 (13)	0.54031 (16)	0.0667 (5)
C8	0.31263 (12)	0.41250 (11)	0.58189 (13)	0.0506 (4)
C9	0.47375 (12)	0.40501 (10)	0.57886 (13)	0.0452 (4)
C10	0.61571 (13)	0.39512 (12)	0.55850 (16)	0.0583 (5)
C11	0.57888 (13)	0.38625 (12)	0.45425 (16)	0.0563 (5)
C12	0.62499 (18)	0.37260 (17)	0.35901 (19)	0.0818 (7)
C13	0.18427 (14)	0.34156 (12)	0.63811 (17)	0.0646 (5)
C14	0.24379 (18)	0.27066 (14)	0.6583 (2)	0.0850 (7)
C15	0.11223 (17)	0.34038 (16)	0.7103 (2)	0.0856 (7)
H1	0.2751	0.4131	0.7309	0.064*
H3	0.2160	0.5213	0.7957	0.073*
H4	0.1303	0.6309	0.7766	0.089*
H6	0.0583	0.5877	0.4605	0.095*
H7	0.1400	0.4765	0.4808	0.080*
H10	0.6782	0.3942	0.5812	0.070*
H13	0.1535	0.3409	0.5626	0.078*
H111	0.4119	0.4175	0.7020	0.060*
H121	0.6896	0.3732	0.3823	0.098*
H122	0.6081	0.4118	0.3062	0.098*
H123	0.6068	0.3241	0.3276	0.098*
H141	0.2729	0.2694	0.7326	0.102*
H142	0.2890	0.2719	0.6126	0.102*
H143	0.2068	0.2262	0.6422	0.102*
H151	0.0750	0.2960	0.6946	0.103*
H152	0.0752	0.3850	0.6972	0.103*
H153	0.1412	0.3393	0.7848	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1126 (6)	0.0730 (4)	0.1748 (9)	0.0221 (3)	0.0210 (5)	0.0226 (5)
S1	0.0557 (3)	0.0783 (3)	0.0340 (2)	−0.0055 (2)	0.0085 (2)	−0.00354 (19)
O1	0.0527 (8)	0.1174 (13)	0.0374 (7)	0.0055 (7)	0.0038 (5)	−0.0021 (6)
N1	0.0439 (8)	0.0725 (9)	0.0325 (7)	0.0020 (6)	0.0070 (5)	−0.0005 (6)
N2	0.0462 (8)	0.0767 (10)	0.0363 (7)	−0.0003 (6)	0.0074 (6)	−0.0030 (6)
C1	0.0451 (10)	0.0762 (12)	0.0382 (8)	0.0032 (8)	0.0052 (7)	0.0008 (8)
C2	0.0412 (9)	0.0713 (11)	0.0466 (9)	−0.0028 (8)	0.0073 (7)	0.0040 (8)
C3	0.0579 (11)	0.0705 (12)	0.0553 (10)	0.0004 (9)	0.0109 (8)	−0.0006 (9)
C4	0.0711 (15)	0.0687 (14)	0.0854 (17)	−0.0069 (10)	0.0233 (12)	−0.0088 (11)
C5	0.0608 (13)	0.0676 (13)	0.0987 (19)	−0.0022 (10)	0.0142 (12)	0.0143 (13)
C6	0.0658 (14)	0.0892 (17)	0.0771 (15)	0.0059 (11)	−0.0015 (11)	0.0222 (13)
C7	0.0589 (11)	0.0826 (14)	0.0546 (11)	0.0032 (10)	−0.0012 (8)	0.0027 (10)
C8	0.0454 (9)	0.0673 (11)	0.0388 (9)	0.0019 (7)	0.0060 (7)	0.0025 (7)
C9	0.0487 (9)	0.0531 (9)	0.0338 (7)	−0.0006 (6)	0.0071 (6)	0.0013 (6)
C10	0.0463 (10)	0.0830 (14)	0.0472 (10)	−0.0028 (8)	0.0127 (8)	−0.0056 (8)
C11	0.0564 (11)	0.0683 (11)	0.0465 (10)	−0.0072 (8)	0.0159 (8)	−0.0059 (8)
C12	0.0754 (15)	0.118 (2)	0.0586 (12)	−0.0162 (14)	0.0299 (11)	−0.0212 (13)
C13	0.0569 (11)	0.0775 (13)	0.0589 (11)	−0.0026 (9)	0.0083 (9)	0.0043 (10)
C14	0.0848 (17)	0.0730 (15)	0.0990 (19)	0.0032 (12)	0.0214 (14)	0.0015 (13)
C15	0.0702 (15)	0.0908 (17)	0.1022 (19)	−0.0038 (12)	0.0331 (13)	0.0192 (14)

Geometric parameters (Å, º) top

Cl1—C5	1.744 (2)	C13—C14	1.529 (3)
S1—C9	1.7227 (17)	C13—C15	1.524 (3)
S1—C11	1.731 (2)	N1—H111	0.860
O1—C8	1.220 (2)	C1—H1	0.980
N1—C8	1.365 (2)	C3—H3	0.930
N1—C9	1.386 (2)	C4—H4	0.930
N2—C9	1.304 (2)	C6—H6	0.930
N2—C10	1.380 (2)	C7—H7	0.930
C1—C2	1.515 (2)	C10—H10	0.930
C1—C8	1.522 (2)	C12—H121	0.960
C1—C13	1.539 (2)	C12—H122	0.960
C2—C3	1.385 (2)	C12—H123	0.960
C2—C7	1.397 (2)	C13—H13	0.980
C3—C4	1.381 (3)	C14—H141	0.960
C4—C5	1.384 (3)	C14—H142	0.960
C5—C6	1.372 (3)	C14—H143	0.960
C6—C7	1.374 (3)	C15—H151	0.960
C10—C11	1.339 (2)	C15—H152	0.960
C11—C12	1.500 (3)	C15—H153	0.960

C9—S1—C11	89.24 (9)	C13—C1—H1	107.7
C8—N1—C9	123.37 (14)	C2—C3—H3	119.1
C9—N2—C10	109.35 (15)	C4—C3—H3	119.1
C2—C1—C8	110.74 (16)	C3—C4—H4	120.6
C2—C1—C13	113.75 (15)	C5—C4—H4	120.6
C8—C1—C13	109.12 (16)	C5—C6—H6	119.9
C1—C2—C3	120.52 (15)	C7—C6—H6	119.9
C1—C2—C7	121.50 (17)	C2—C7—H7	119.7
C3—C2—C7	117.97 (19)	C6—C7—H7	119.7
C2—C3—C4	121.75 (19)	N2—C10—H10	121.4
C3—C4—C5	118.8 (2)	C11—C10—H10	121.4
Cl1—C5—C4	119.5 (2)	C11—C12—H121	109.5
Cl1—C5—C6	119.8 (2)	C11—C12—H122	109.5
C4—C5—C6	120.6 (2)	C11—C12—H123	109.5
C5—C6—C7	120.1 (2)	H121—C12—H122	109.5
C2—C7—C6	120.7 (2)	H121—C12—H123	109.5
O1—C8—N1	121.86 (17)	H122—C12—H123	109.5
O1—C8—C1	122.81 (15)	C1—C13—H13	108.2
N1—C8—C1	115.30 (14)	C14—C13—H13	108.2
S1—C9—N1	123.45 (12)	C15—C13—H13	108.2
S1—C9—N2	115.22 (14)	C13—C14—H141	109.5
N1—C9—N2	121.32 (15)	C13—C14—H142	109.5
N2—C10—C11	117.29 (18)	C13—C14—H143	109.5
S1—C11—C10	108.91 (16)	H141—C14—H142	109.5
S1—C11—C12	122.03 (14)	H141—C14—H143	109.5
C10—C11—C12	129.06 (19)	H142—C14—H143	109.5
C1—C13—C14	110.73 (18)	C13—C15—H151	109.5
C1—C13—C15	111.30 (18)	C13—C15—H152	109.5
C14—C13—C15	110.0 (2)	C13—C15—H153	109.5
C8—N1—H111	118.3	H151—C15—H152	109.5
C9—N1—H111	118.3	H151—C15—H153	109.5
C2—C1—H1	107.7	H152—C15—H153	109.5
C8—C1—H1	107.7

C9—S1—C11—C10	−0.73 (16)	C13—C1—C2—C7	−65.9 (2)
C9—S1—C11—C12	178.9 (2)	C8—C1—C13—C14	57.6 (2)
C11—S1—C9—N1	−178.04 (16)	C8—C1—C13—C15	−179.67 (16)
C11—S1—C9—N2	0.70 (15)	C13—C1—C8—O1	60.1 (2)
C8—N1—C9—S1	−1.7 (2)	C13—C1—C8—N1	−118.44 (17)
C8—N1—C9—N2	179.66 (17)	C1—C2—C3—C4	−178.9 (2)
C9—N1—C8—O1	−4.1 (2)	C1—C2—C7—C6	−180.0 (2)
C9—N1—C8—C1	174.50 (16)	C3—C2—C7—C6	0.7 (3)
C9—N2—C10—C11	−0.2 (2)	C7—C2—C3—C4	0.4 (3)
C10—N2—C9—S1	−0.4 (2)	C2—C3—C4—C5	−1.3 (3)
C10—N2—C9—N1	178.33 (16)	C3—C4—C5—Cl1	−178.89 (19)
C2—C1—C8—O1	−65.9 (2)	C3—C4—C5—C6	1.1 (3)
C2—C1—C8—N1	115.61 (17)	Cl1—C5—C6—C7	179.97 (13)
C8—C1—C2—C3	−123.34 (19)	C4—C5—C6—C7	−0.0 (3)
C8—C1—C2—C7	57.4 (2)	C5—C6—C7—C2	−0.9 (3)
C2—C1—C13—C14	−178.17 (17)	N2—C10—C11—S1	0.7 (2)
C2—C1—C13—C15	−55.5 (2)	N2—C10—C11—C12	−178.9 (2)
C13—C1—C2—C3	113.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H111···N2ⁱ	0.86	2.08	2.929 (2)	168

Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇ClN₂OS
M_r	308.83
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	14.9649 (6), 17.6062 (7), 12.5606 (5)
β (°)	99.9482 (11)
V (Å³)	3259.6 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.41 × 0.33 × 0.26

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.858, 0.911
No. of measured, independent and observed [F² > 2σ(F²)] reflections	15655, 3708, 2559
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.172, 1.01
No. of reflections	3708
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), CrystalStructure.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H111···N2ⁱ	0.86	2.08	2.929 (2)	168

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

The authors are grateful for support from the National Natural Science Foundation of China (No. 30700532) and also thank Professor Jian-Ming Gu for help with the analysis of the crystal data.

References

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