2-Chloro-N-isopropyl-N-phenyl­acetamide

Yuan, M.-S.; Li, Z.; Wang, Q.

doi:10.1107/S1600536810027157

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2017

https://doi.org/10.1107/S1600536810027157

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2-Chloro-N-isopropyl-N-phenylacetamide

Mao-Sen Yuan,^a ^* Zhi-peng Li ^b and Qi Wang ^a

^aCollege of Science, Northwest A&F University, Yangling 712100, Shannxi Province, People's Republic of China, and ^bCollege of Life Sciences, Northwest A&F University, Yangling 712100, Shannxi Province, People's Republic of China
^*Correspondence e-mail: yuanms@nwsuaf.edu.cn

(Received 26 June 2010; accepted 8 July 2010; online 14 July 2010)

In the title compound, C₁₁H₁₄ClNO, the herbicide propachlor, there are significant differences between the three N—C bond lengths [N—C_carbonyl = 1.354 (3) Å, N—C_phenyl = 1.444 (2) Å and N—C_isopropyl = 1.496 (3) Å], indicating the presence of π delocalization involving the carbonyl group. The N atom lies 0.074 (2) Å from the plane defined by the the three bonded C atoms.

Related literature

For studies of propachlor and its derivatives, see: Dhillon & Anderson (1972 ); Kleudgen (1980 ).

Experimental

Crystal data

C₁₁H₁₄ClNO
M_r = 211.68
Monoclinic, P 2₁ /n
a = 11.9190 (11) Å
b = 7.8042 (8) Å
c = 12.3789 (13) Å
β = 98.963 (1)°
V = 1137.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 298 K
0.47 × 0.45 × 0.44 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.870, T_max = 0.878
5426 measured reflections
2004 independent reflections
1501 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.03
2004 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810027157/zs2048sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027157/zs2048Isup2.hkl

checkCIF report

Comment top

Propachlor (2-chloro-N-isopropyl-N-phenylacetamide) and its derivatives have been widely studied as a pre-emergent herbicide used to control broadleaf weeds and grasses (Dhillon et al., 1972; Kleudgen, 1980). Propachlor may also be used as a precursor in the synthesis of indole-2-one compounds and in the course of exploring new indole-2-one compounds, we synthesized the title compound C₁₁H₁₄ClNO (I), the structure of which is reported here.

In structure of (I) (Fig. 1), there are obvious differences between the three C—N bond lengths (N—C_carbonyl, 1.354 (3) Å; N—C_phenyl, 1.444 (2) Å; N—C_isopropyl, 1.496 (3) Å, indicating the presence of π delocalization involving the carbonyl group. Also N1 lies close to the plane defined by the three bonded carbon atoms C1, C3 and C9 [0.074 (2) Å].

As expected, there are no classic hydrogen bonds in the structure (Fig. 2). However, there is a weak intermolecular aliphatic C11—H11A···O1ⁱ interaction [symmetry code: (i) -x + 1/2, y - 1/2, -z + 1/2] stabilizing the packing. This intermolecular hydrogen bond is characterized by the parameters 0.96 Å (C11—H11A) and 2.56 Å (H11A···O1ⁱ).

Related literature top

For studies of propachlor and its derivatives, see: Dhillon & Anderson (1972); Kleudgen (1980).

Experimental top

N-Isopropylbenzenamine (1.00 g, 7.41 mmol) was dissolved in toluene (5.0 mL) and cooled to 273 K, after which a solution of 2-chloroacetyl chloride (0.90 g, 8.03 mmol) in toluene (5.0 mL) was slowly added over 0.5 h. with stirring. The mixture was then refluxed for 2 h. then slowly cooled to room temperature over 8 h. Colorless block crystals of (I) were formed (1.33 g, yield 85%).

Structure description top

For studies of propachlor and its derivatives, see: Dhillon & Anderson (1972); Kleudgen (1980).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular comformation and atom numbering scheme for (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular packing of (I) viewed down the b axis of the unit cell.

2-Chloro-N-isopropyl-N-phenylacetamide top

Crystal data top

C₁₁H₁₄ClNO	F(000) = 448
M_r = 211.68	D_x = 1.236 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2899 reflections
a = 11.9190 (11) Å	θ = 2.2–25.0°
b = 7.8042 (8) Å	µ = 0.30 mm⁻¹
c = 12.3789 (13) Å	T = 298 K
β = 98.963 (1)°	Block, colorless
V = 1137.4 (2) Å³	0.47 × 0.45 × 0.44 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2004 independent reflections
Radiation source: fine-focus sealed tube	1501 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→12
T_min = 0.870, T_max = 0.878	k = −9→8
5426 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0469P)² + 0.4408P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2004 reflections	Δρ_max = 0.21 e Å⁻³
130 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.079 (5)

Crystal data top

C₁₁H₁₄ClNO	V = 1137.4 (2) Å³
M_r = 211.68	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.9190 (11) Å	µ = 0.30 mm⁻¹
b = 7.8042 (8) Å	T = 298 K
c = 12.3789 (13) Å	0.47 × 0.45 × 0.44 mm
β = 98.963 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2004 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1501 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.878	R_int = 0.025
5426 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
2004 reflections	Δρ_min = −0.19 e Å⁻³
130 parameters

Special details top

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
Cl1	0.57852 (5)	0.22476 (9)	0.44873 (5)	0.0711 (3)
N1	0.25393 (14)	0.3526 (2)	0.40187 (13)	0.0483 (4)
O1	0.40481 (14)	0.4455 (2)	0.32694 (12)	0.0662 (5)
C1	0.36637 (17)	0.3629 (3)	0.39670 (16)	0.0475 (5)
C2	0.44299 (18)	0.2648 (3)	0.48500 (18)	0.0543 (6)
H2A	0.4074	0.1566	0.4980	0.065*
H2B	0.4520	0.3301	0.5525	0.065*
C3	0.21346 (16)	0.2664 (3)	0.49159 (15)	0.0438 (5)
C4	0.17401 (18)	0.0998 (3)	0.47994 (18)	0.0548 (6)
H4	0.1734	0.0423	0.4140	0.066*
C5	0.1354 (2)	0.0186 (3)	0.5666 (2)	0.0674 (7)
H5	0.1097	−0.0939	0.5592	0.081*
C6	0.1349 (2)	0.1042 (4)	0.6635 (2)	0.0691 (7)
H6	0.1073	0.0504	0.7211	0.083*
C7	0.1751 (2)	0.2691 (4)	0.67528 (19)	0.0701 (7)
H7	0.1757	0.3260	0.7414	0.084*
C8	0.21471 (19)	0.3513 (3)	0.58983 (17)	0.0586 (6)
H8	0.2420	0.4629	0.5983	0.070*
C9	0.1714 (2)	0.4559 (3)	0.32459 (18)	0.0641 (7)
H9	0.2083	0.4850	0.2615	0.077*
C10	0.1415 (3)	0.6210 (3)	0.3759 (3)	0.0939 (10)
H10A	0.1033	0.5964	0.4368	0.141*
H10B	0.0926	0.6875	0.3228	0.141*
H10C	0.2097	0.6845	0.4006	0.141*
C11	0.0654 (3)	0.3538 (4)	0.2827 (3)	0.1013 (11)
H11A	0.0865	0.2471	0.2530	0.152*
H11B	0.0186	0.4179	0.2267	0.152*
H11C	0.0240	0.3318	0.3418	0.152*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0516 (4)	0.0819 (5)	0.0834 (5)	0.0023 (3)	0.0212 (3)	−0.0015 (3)
N1	0.0526 (10)	0.0511 (10)	0.0426 (9)	0.0058 (8)	0.0115 (7)	0.0076 (8)
O1	0.0760 (11)	0.0647 (11)	0.0635 (9)	−0.0032 (8)	0.0288 (8)	0.0168 (8)
C1	0.0592 (13)	0.0403 (11)	0.0455 (11)	−0.0013 (9)	0.0157 (10)	−0.0021 (9)
C2	0.0477 (12)	0.0591 (14)	0.0588 (13)	0.0012 (10)	0.0167 (10)	0.0089 (11)
C3	0.0410 (10)	0.0493 (12)	0.0420 (10)	0.0039 (9)	0.0091 (8)	0.0049 (9)
C4	0.0519 (12)	0.0549 (14)	0.0582 (13)	−0.0021 (10)	0.0106 (10)	−0.0024 (11)
C5	0.0572 (14)	0.0606 (15)	0.0859 (17)	−0.0076 (11)	0.0157 (12)	0.0164 (14)
C6	0.0581 (14)	0.090 (2)	0.0622 (15)	−0.0004 (13)	0.0178 (11)	0.0268 (15)
C7	0.0761 (17)	0.091 (2)	0.0456 (13)	−0.0016 (14)	0.0178 (12)	0.0005 (13)
C8	0.0685 (14)	0.0576 (14)	0.0514 (12)	−0.0041 (11)	0.0150 (10)	−0.0015 (11)
C9	0.0692 (15)	0.0715 (17)	0.0521 (12)	0.0177 (12)	0.0110 (11)	0.0201 (12)
C10	0.095 (2)	0.0512 (16)	0.122 (2)	0.0114 (15)	−0.0266 (18)	0.0041 (16)
C11	0.112 (2)	0.078 (2)	0.094 (2)	0.0226 (18)	−0.0480 (18)	−0.0207 (17)

Geometric parameters (Å, º) top

Cl1—C2	1.771 (2)	C6—C7	1.374 (4)
N1—C1	1.354 (3)	C6—H6	0.9300
N1—C3	1.444 (2)	C7—C8	1.381 (3)
N1—C9	1.496 (3)	C7—H7	0.9300
O1—C1	1.222 (2)	C8—H8	0.9300
C1—C2	1.518 (3)	C9—C10	1.503 (4)
C2—H2A	0.9700	C9—C11	1.515 (4)
C2—H2B	0.9700	C9—H9	0.9800
C3—C4	1.383 (3)	C10—H10A	0.9600
C3—C8	1.383 (3)	C10—H10B	0.9600
C4—C5	1.385 (3)	C10—H10C	0.9600
C4—H4	0.9300	C11—H11A	0.9600
C5—C6	1.373 (4)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600

C1—N1—C3	121.03 (16)	C6—C7—C8	120.6 (2)
C1—N1—C9	119.66 (17)	C6—C7—H7	119.7
C3—N1—C9	118.53 (16)	C8—C7—H7	119.7
O1—C1—N1	123.2 (2)	C7—C8—C3	119.5 (2)
O1—C1—C2	121.67 (19)	C7—C8—H8	120.2
N1—C1—C2	115.15 (16)	C3—C8—H8	120.2
C1—C2—Cl1	112.14 (14)	N1—C9—C10	111.53 (19)
C1—C2—H2A	109.2	N1—C9—C11	111.5 (2)
Cl1—C2—H2A	109.2	C10—C9—C11	110.8 (2)
C1—C2—H2B	109.2	N1—C9—H9	107.6
Cl1—C2—H2B	109.2	C10—C9—H9	107.6
H2A—C2—H2B	107.9	C11—C9—H9	107.6
C4—C3—C8	119.95 (19)	C9—C10—H10A	109.5
C4—C3—N1	120.46 (18)	C9—C10—H10B	109.5
C8—C3—N1	119.59 (19)	H10A—C10—H10B	109.5
C3—C4—C5	119.9 (2)	C9—C10—H10C	109.5
C3—C4—H4	120.1	H10A—C10—H10C	109.5
C5—C4—H4	120.1	H10B—C10—H10C	109.5
C6—C5—C4	120.1 (2)	C9—C11—H11A	109.5
C6—C5—H5	119.9	C9—C11—H11B	109.5
C4—C5—H5	119.9	H11A—C11—H11B	109.5
C5—C6—C7	120.0 (2)	C9—C11—H11C	109.5
C5—C6—H6	120.0	H11A—C11—H11C	109.5
C7—C6—H6	120.0	H11B—C11—H11C	109.5

C3—N1—C1—O1	−174.27 (19)	N1—C3—C4—C5	−179.95 (19)
C9—N1—C1—O1	−4.6 (3)	C3—C4—C5—C6	0.8 (3)
C3—N1—C1—C2	5.3 (3)	C4—C5—C6—C7	−1.5 (4)
C9—N1—C1—C2	174.98 (19)	C5—C6—C7—C8	1.0 (4)
O1—C1—C2—Cl1	−20.0 (3)	C6—C7—C8—C3	0.1 (4)
N1—C1—C2—Cl1	160.48 (15)	C4—C3—C8—C7	−0.8 (3)
C1—N1—C3—C4	−98.8 (2)	N1—C3—C8—C7	179.5 (2)
C9—N1—C3—C4	91.4 (2)	C1—N1—C9—C10	−96.3 (2)
C1—N1—C3—C8	81.0 (3)	C3—N1—C9—C10	73.7 (3)
C9—N1—C3—C8	−88.8 (2)	C1—N1—C9—C11	139.2 (2)
C8—C3—C4—C5	0.3 (3)	C3—N1—C9—C11	−50.8 (3)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄ClNO
M_r	211.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.9190 (11), 7.8042 (8), 12.3789 (13)
β (°)	98.963 (1)
V (Å³)	1137.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.47 × 0.45 × 0.44

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.870, 0.878
No. of measured, independent and observed [I > 2σ(I)] reflections	5426, 2004, 1501
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.03
No. of reflections	2004
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the PhD Programs Foundation of the Ministry of Education of China (No. 20090204120033)

References

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Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Kleudgen, H. K. (1980). Weed Res. 20, 41–46. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar