2-(4-Chloro­phen­yl)acetamide

Abstract

In the title compound, C₈H₈ClNO, the acetamide group is twisted out the benzene plane with a dihedral angle of 83.08 (1)°. In the crystal, mol­ecules are linked by N—H⋯O hydrogen bonds, forming layers parallel to the ab plane.

Related literature

For details of the nitrile hydrolysis of the same substrate (4-chlorobenzonitrile) by another method, see: Moorthy & Singhal (2005 ▶).

Experimental

Crystal data

• C₈H₈ClNO

• M _r = 169.60

• Orthorhombic,

• a = 4.917 (2) Å

• b = 6.033 (4) Å

• c = 26.680 (12) Å

• V = 791.5 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.42 mm⁻¹

• T = 293 K

• 0.29 × 0.22 × 0.07 mm

Data collection

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.887, T _max = 0.970

• 7733 measured reflections

• 1807 independent reflections

• 1451 reflections with I > 2σ(I)

• R _int = 0.041

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.083

• S = 1.05

• 1807 reflections

• 108 parameters

• 2 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

• Absolute structure: Flack (1983 ▶), 704 Friedel pairs

• Flack parameter: −0.12 (8)

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); 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: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811046836/cv5191Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O1i	0.88 (1)	2.05 (1)	2.911 (2)	165 (2)
N1—H12⋯O1ii	0.89 (1)	2.22 (1)	3.064 (3)	157 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The title compound is formed by hydrolysis of appropriate nitriles (Moorthy et al., 2005), while the final product of hydrolysis of nitriles should be carboxylic acid. In this paper, we report the synthesis and the crystal structure of the title compound prepared from 4-cyanobenzylchloride under solvothermal condition.

In the title molecule (Fig.1), the acetamide group is twisted out the benzene plane with a dihedral angle of 83.08 (1) °. In the crystal packing, the molecules are linked by N—H···O hydrogen bonds to form layers parallel to ab plane (Fig. 2, Table 1).

Experimental

A mixture of NaN₃ (0.39 g, 6 mmol), CuCl₂^.2H₂O (0.684 g, 4 mmol), and 4-cyanobenzylchloride (0.606 g, 4 mmol) was sealed in a 15 ml teflon-lined reactor and heated in an oven at 150 ° C for 72 hrs and slowly cooled to room temperature. The resulting mixture was washed with water, and pale yellow blocklike crystals were collected (yeild 31%).

Refinement

N-bound H atoms were located in a differece Fourier map and refined with restraint of N—H = 0.89 (1) Å. C-bound H atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic); C—H = 0.97 Å (methylene), and with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level.

Fig. 2.

A portion of the crystal packing, showing a two-dimensional structure formed by N—H···O hydrogen bonds (dashed lines).

Crystal data

C8H8ClNO	F(000) = 352
Mr = 169.60	Dx = 1.423 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5994 reflections
a = 4.917 (2) Å	θ = 3.1–27.4°
b = 6.033 (4) Å	µ = 0.42 mm−1
c = 26.680 (12) Å	T = 293 K
V = 791.5 (7) Å3	Block, colorless
Z = 4	0.29 × 0.22 × 0.07 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	1807 independent reflections
Radiation source: fine-focus sealed tube	1451 reflections with I > 2σ(I)
graphite	Rint = 0.041
ω scan	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
Tmin = 0.887, Tmax = 0.970	k = −7→7
7733 measured reflections	l = −34→33

Refinement

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.036P)2 + 0.1017P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1807 reflections	Δρmax = 0.17 e Å−3
108 parameters	Δρmin = −0.17 e Å−3
2 restraints	Absolute structure: Flack (1983), 704 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.12 (8)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3632 (4)	0.5073 (3)	0.79843 (7)	0.0335 (4)
C2	0.2527 (4)	0.3677 (5)	0.84087 (10)	0.0603 (7)
H2A	0.1560	0.4638	0.8639	0.072*
H2B	0.1222	0.2633	0.8272	0.072*
C3	0.4640 (4)	0.2408 (4)	0.86973 (8)	0.0429 (5)
C4	0.5575 (5)	0.0374 (4)	0.85279 (8)	0.0487 (6)
H4	0.4907	−0.0195	0.8228	0.058*
C5	0.7475 (5)	−0.0822 (3)	0.87944 (8)	0.0451 (5)
H5	0.8079	−0.2185	0.8676	0.054*
C6	0.8470 (4)	0.0017 (4)	0.92375 (8)	0.0410 (5)
C7	0.7620 (5)	0.2049 (4)	0.94146 (8)	0.0472 (6)
H7	0.8324	0.2622	0.9711	0.057*
C8	0.5697 (5)	0.3221 (4)	0.91430 (8)	0.0487 (5)
H8	0.5100	0.4586	0.9262	0.058*
Cl1	1.08553 (13)	−0.14906 (11)	0.95804 (2)	0.0605 (2)
N1	0.1788 (3)	0.6234 (4)	0.77353 (7)	0.0441 (4)
H11	0.004 (2)	0.613 (4)	0.7811 (8)	0.046 (6)*
H12	0.225 (5)	0.714 (4)	0.7485 (7)	0.064 (8)*
O1	0.6073 (3)	0.5149 (3)	0.78808 (5)	0.0435 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0263 (9)	0.0376 (11)	0.0367 (10)	−0.0005 (9)	0.0007 (8)	−0.0027 (8)
C2	0.0291 (11)	0.0819 (19)	0.0699 (15)	0.0050 (12)	0.0050 (11)	0.0347 (15)
C3	0.0310 (11)	0.0528 (13)	0.0449 (11)	0.0000 (9)	0.0035 (9)	0.0145 (9)
C4	0.0493 (13)	0.0554 (14)	0.0416 (11)	−0.0093 (12)	−0.0077 (11)	−0.0001 (10)
C5	0.0511 (13)	0.0368 (12)	0.0475 (12)	0.0016 (9)	0.0072 (11)	−0.0041 (9)
C6	0.0381 (11)	0.0444 (12)	0.0406 (10)	0.0018 (10)	0.0046 (9)	0.0071 (9)
C7	0.0514 (13)	0.0514 (14)	0.0387 (11)	0.0009 (10)	−0.0027 (10)	−0.0056 (10)
C8	0.0503 (13)	0.0433 (13)	0.0525 (12)	0.0118 (12)	0.0069 (12)	−0.0003 (10)
Cl1	0.0520 (3)	0.0695 (4)	0.0598 (3)	0.0147 (3)	−0.0015 (3)	0.0194 (3)
N1	0.0243 (8)	0.0587 (12)	0.0494 (10)	−0.0006 (8)	0.0013 (8)	0.0149 (10)
O1	0.0237 (6)	0.0529 (9)	0.0538 (8)	−0.0038 (7)	0.0051 (7)	0.0046 (7)

Geometric parameters (Å, °)

C1—O1	1.232 (2)	C5—C6	1.376 (3)
C1—N1	1.324 (3)	C5—H5	0.9300
C1—C2	1.512 (3)	C6—C7	1.379 (3)
C2—C3	1.503 (3)	C6—Cl1	1.744 (2)
C2—H2A	0.9700	C7—C8	1.386 (3)
C2—H2B	0.9700	C7—H7	0.9300
C3—C4	1.386 (3)	C8—H8	0.9300
C3—C8	1.387 (3)	N1—H11	0.883 (10)
C4—C5	1.378 (3)	N1—H12	0.892 (10)
C4—H4	0.9300
O1—C1—N1	122.34 (19)	C6—C5—C4	119.5 (2)
O1—C1—C2	122.57 (18)	C6—C5—H5	120.3
N1—C1—C2	115.08 (17)	C4—C5—H5	120.3
C3—C2—C1	114.78 (17)	C5—C6—C7	120.9 (2)
C3—C2—H2A	108.6	C5—C6—Cl1	119.88 (18)
C1—C2—H2A	108.6	C7—C6—Cl1	119.21 (17)
C3—C2—H2B	108.6	C6—C7—C8	118.8 (2)
C1—C2—H2B	108.6	C6—C7—H7	120.6
H2A—C2—H2B	107.5	C8—C7—H7	120.6
C4—C3—C8	117.9 (2)	C7—C8—C3	121.6 (2)
C4—C3—C2	120.9 (2)	C7—C8—H8	119.2
C8—C3—C2	121.2 (2)	C3—C8—H8	119.2
C5—C4—C3	121.3 (2)	C1—N1—H11	120.9 (16)
C5—C4—H4	119.3	C1—N1—H12	121.7 (18)
C3—C4—H4	119.3	H11—N1—H12	117 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O1i	0.88 (1)	2.05 (1)	2.911 (2)	165 (2)
N1—H12···O1ii	0.89 (1)	2.22 (1)	3.064 (3)	157 (2)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+3/2.