organic compounds
2-(4-Chlorophenyl)acetamide
aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
*Correspondence e-mail: hgf1000@163.com
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
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Data collection: RAPID-AUTO (Rigaku, 1998); cell 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.
Supporting information
https://doi.org/10.1107/S1600536811046836/cv5191sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046836/cv5191Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811046836/cv5191Isup3.cml
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%).
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 Uiso(H) = 1.2Ueq(C).
The title compound is formed by hydrolysis of appropriate
(Moorthy et al., 2005), while the final product of hydrolysis of should be carboxylic acid. In this paper, we report the synthesis and the 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).
For details of the related nitrile hydrolysis, see: Moorthy & Singhal (2005).
Data collection: RAPID-AUTO (Rigaku, 1998); cell
RAPID-AUTO (Rigaku, 1998); 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 (Sheldrick, 2008).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 |
Rigaku R-AXIS RAPID diffractometer | 1807 independent reflections |
Radiation source: fine-focus sealed tube | 1451 reflections with I > 2σ(I) |
Graphite monochromator | 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 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 | Absolute structure parameter: −0.12 (8) |
C8H8ClNO | V = 791.5 (7) Å3 |
Mr = 169.60 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.917 (2) Å | µ = 0.42 mm−1 |
b = 6.033 (4) Å | T = 293 K |
c = 26.680 (12) Å | 0.29 × 0.22 × 0.07 mm |
Rigaku R-AXIS RAPID diffractometer | 1807 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1451 reflections with I > 2σ(I) |
Tmin = 0.887, Tmax = 0.970 | Rint = 0.041 |
7733 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | Δρmax = 0.17 e Å−3 |
S = 1.05 | Δρmin = −0.17 e Å−3 |
1807 reflections | Absolute structure: Flack (1983), 704 Friedel pairs |
108 parameters | Absolute structure parameter: −0.12 (8) |
2 restraints |
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. |
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) |
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) |
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) |
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. |
Experimental details
Crystal data | |
Chemical formula | C8H8ClNO |
Mr | 169.60 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 4.917 (2), 6.033 (4), 26.680 (12) |
V (Å3) | 791.5 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.29 × 0.22 × 0.07 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.887, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7733, 1807, 1451 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.083, 1.05 |
No. of reflections | 1807 |
No. of parameters | 108 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Absolute structure | Flack (1983), 704 Friedel pairs |
Absolute structure parameter | −0.12 (8) |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···O1i | 0.883 (10) | 2.049 (11) | 2.911 (2) | 165 (2) |
N1—H12···O1ii | 0.892 (10) | 2.221 (14) | 3.064 (3) | 157 (2) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+3/2. |
Acknowledgements
The authors thank Heilongjiang University for supporting this work.
References
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Moorthy, J. N. & Singhal, N. (2005). J. Org. Chem. 70, 1926–1929. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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).