organic compounds
2,2,2-Trichloro-N-(2,5-dimethylphenyl)acetamide
aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
*Correspondence e-mail: gowdabt@yahoo.com
The N—H bond in the title compound, C10H10Cl3NO, is syn to the 2-methyl and anti to the 5-methyl substituent of the aromatic ring. Adjacent molecules are linked into chains through N—H⋯O hydrogen bonding. Two Cl atoms are each disordered equally over two sites.
Related literature
For related literature, see: Gowda, Foro & Fuess (2007); Gowda, Kožíšek et al. (2007); Shilpa & Gowda (2007).
Experimental
Crystal data
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Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808009264/ng2441sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808009264/ng2441Isup2.hkl
The title compound was prepared according to the literature method (Shilpa and Gowda, 2007). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Shilpa and Gowda, 2007). Single crystals of the title compound were obtained from an ethanolic solution and used for X-ray diffraction studies at room temperature.
The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.96 Å, N—H = 0.86 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent atom).
The Cl atoms of CCl3 group are disordered and Cl1 and Cl3 were refined using a split model with site-occupation factors 0.5:0.5. No reliable disorder model could be produced for Cl2. The C—Cl distances were restrained to 1.77 (2) Å and the distances in the disordered groups were restrained to be equal.
The compound is a weak anamalous scatterer with minor intensity at high θ value. The low fraction of unique data is above the 2σ level (30°).
Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell
CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C10H10Cl3NO | F(000) = 544 |
Mr = 266.54 | Dx = 1.514 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1061 reflections |
a = 4.9173 (9) Å | θ = 2.6–28.1° |
b = 11.290 (1) Å | µ = 0.76 mm−1 |
c = 21.070 (2) Å | T = 299 K |
V = 1169.7 (3) Å3 | Prism, colourless |
Z = 4 | 0.16 × 0.12 × 0.06 mm |
Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector | 2314 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 703 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
Rotation method data acquisition using ω and phi scans. | θmax = 26.4°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | h = −6→6 |
Tmin = 0.889, Tmax = 0.956 | k = −14→13 |
6121 measured reflections | l = −26→23 |
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)] = 0.088 | H-atom parameters constrained |
wR(F2) = 0.309 | w = 1/[σ2(Fo2) + (0.1675P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.86 | (Δ/σ)max = 0.003 |
2314 reflections | Δρmax = 0.27 e Å−3 |
154 parameters | Δρmin = −0.76 e Å−3 |
37 restraints | Absolute structure: Flack (1983), 887 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.4 (4) |
C10H10Cl3NO | V = 1169.7 (3) Å3 |
Mr = 266.54 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.9173 (9) Å | µ = 0.76 mm−1 |
b = 11.290 (1) Å | T = 299 K |
c = 21.070 (2) Å | 0.16 × 0.12 × 0.06 mm |
Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector | 2314 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 703 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.956 | Rint = 0.071 |
6121 measured reflections |
R[F2 > 2σ(F2)] = 0.088 | H-atom parameters constrained |
wR(F2) = 0.309 | Δρmax = 0.27 e Å−3 |
S = 0.86 | Δρmin = −0.76 e Å−3 |
2314 reflections | Absolute structure: Flack (1983), 887 Friedel pairs |
154 parameters | Absolute structure parameter: −0.4 (4) |
37 restraints |
Experimental. 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1A | 0.4909 (19) | 0.3895 (7) | 0.5055 (3) | 0.096 (2) | 0.50 |
Cl1B | 0.301 (3) | 0.3888 (10) | 0.5125 (4) | 0.139 (4) | 0.50 |
Cl2 | 0.0276 (14) | 0.5253 (7) | 0.5201 (3) | 0.218 (3) | |
Cl3A | 0.459 (2) | 0.6280 (6) | 0.4526 (3) | 0.102 (2) | 0.50 |
Cl3B | 0.226 (2) | 0.6324 (7) | 0.4737 (5) | 0.141 (3) | 0.50 |
O6 | −0.0518 (17) | 0.4448 (7) | 0.3920 (4) | 0.092 (3) | |
N7 | 0.3670 (16) | 0.4054 (7) | 0.3571 (4) | 0.069 (2) | |
H7N | 0.5356 | 0.4163 | 0.3662 | 0.083* | |
C4 | 0.311 (2) | 0.4931 (7) | 0.4592 (4) | 0.082 (3) | |
C5 | 0.180 (3) | 0.4444 (9) | 0.4003 (6) | 0.075 (3) | |
C8 | 0.308 (2) | 0.3488 (8) | 0.2991 (4) | 0.055 (3) | |
C9 | 0.4334 (19) | 0.2416 (9) | 0.2866 (5) | 0.062 (3) | |
C10 | 0.358 (2) | 0.1877 (10) | 0.2267 (5) | 0.079 (3) | |
H10 | 0.4336 | 0.1151 | 0.2154 | 0.095* | |
C11 | 0.178 (2) | 0.2420 (10) | 0.1863 (4) | 0.067 (3) | |
H11 | 0.1371 | 0.2054 | 0.1480 | 0.080* | |
C12 | 0.055 (2) | 0.3486 (10) | 0.2002 (5) | 0.069 (3) | |
C13 | 0.125 (2) | 0.4011 (9) | 0.2572 (4) | 0.062 (3) | |
H13 | 0.0466 | 0.4735 | 0.2679 | 0.074* | |
C14 | 0.624 (2) | 0.1827 (8) | 0.3309 (5) | 0.075 (3) | |
H14A | 0.5312 | 0.1655 | 0.3700 | 0.090* | |
H14B | 0.7750 | 0.2341 | 0.3392 | 0.090* | |
H14C | 0.6878 | 0.1103 | 0.3123 | 0.090* | |
C15 | −0.138 (2) | 0.4037 (11) | 0.1548 (5) | 0.091 (3) | |
H15A | −0.2838 | 0.3497 | 0.1462 | 0.109* | |
H15B | −0.0441 | 0.4218 | 0.1160 | 0.109* | |
H15C | −0.2094 | 0.4753 | 0.1727 | 0.109* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1A | 0.116 (6) | 0.109 (5) | 0.063 (3) | 0.023 (5) | 0.000 (4) | −0.003 (3) |
Cl1B | 0.172 (8) | 0.151 (7) | 0.093 (5) | −0.036 (7) | 0.005 (6) | 0.037 (5) |
Cl2 | 0.213 (6) | 0.278 (7) | 0.163 (4) | 0.011 (6) | 0.007 (4) | −0.053 (4) |
Cl3A | 0.135 (6) | 0.086 (4) | 0.086 (4) | −0.038 (4) | 0.016 (4) | −0.025 (3) |
Cl3B | 0.151 (7) | 0.117 (6) | 0.154 (6) | 0.018 (6) | −0.027 (6) | −0.049 (5) |
O6 | 0.052 (4) | 0.127 (7) | 0.099 (5) | 0.011 (5) | −0.007 (4) | −0.040 (5) |
N7 | 0.049 (5) | 0.068 (5) | 0.092 (6) | −0.004 (5) | −0.014 (5) | 0.016 (5) |
C4 | 0.091 (8) | 0.070 (7) | 0.084 (7) | 0.002 (7) | −0.025 (7) | −0.019 (6) |
C5 | 0.056 (7) | 0.081 (8) | 0.088 (7) | 0.011 (7) | −0.018 (7) | −0.019 (6) |
C8 | 0.055 (6) | 0.061 (6) | 0.048 (5) | −0.009 (6) | 0.004 (6) | −0.005 (5) |
C9 | 0.045 (5) | 0.056 (6) | 0.086 (7) | 0.011 (6) | 0.004 (6) | 0.018 (6) |
C10 | 0.079 (8) | 0.064 (7) | 0.095 (8) | −0.004 (7) | 0.000 (7) | −0.012 (6) |
C11 | 0.077 (8) | 0.064 (7) | 0.061 (6) | −0.004 (7) | 0.005 (6) | 0.005 (5) |
C12 | 0.063 (7) | 0.078 (8) | 0.066 (6) | −0.016 (7) | −0.003 (6) | 0.022 (6) |
C13 | 0.062 (6) | 0.062 (5) | 0.062 (6) | 0.006 (6) | −0.005 (6) | 0.010 (5) |
C14 | 0.073 (7) | 0.050 (6) | 0.102 (7) | 0.001 (7) | −0.004 (7) | 0.000 (6) |
C15 | 0.080 (8) | 0.119 (9) | 0.074 (6) | −0.001 (9) | −0.017 (7) | 0.019 (7) |
Cl1A—C4 | 1.761 (11) | C10—C11 | 1.373 (14) |
Cl1B—C4 | 1.628 (11) | C10—H10 | 0.9300 |
Cl2—C4 | 1.931 (10) | C11—C12 | 1.378 (13) |
Cl3A—C4 | 1.693 (10) | C11—H11 | 0.9300 |
Cl3B—C4 | 1.656 (10) | C12—C13 | 1.382 (14) |
O6—C5 | 1.151 (11) | C12—C15 | 1.484 (14) |
N7—C5 | 1.367 (13) | C13—H13 | 0.9300 |
N7—C8 | 1.411 (11) | C14—H14A | 0.9600 |
N7—H7N | 0.8600 | C14—H14B | 0.9600 |
C4—C5 | 1.503 (13) | C14—H14C | 0.9600 |
C8—C9 | 1.383 (12) | C15—H15A | 0.9600 |
C8—C13 | 1.393 (13) | C15—H15B | 0.9600 |
C9—C10 | 1.449 (14) | C15—H15C | 0.9600 |
C9—C14 | 1.480 (12) | ||
C5—N7—C8 | 125.7 (8) | C10—C9—C14 | 121.5 (9) |
C5—N7—H7N | 117.1 | C11—C10—C9 | 121.1 (10) |
C8—N7—H7N | 117.1 | C11—C10—H10 | 119.5 |
C5—C4—Cl1B | 106.9 (8) | C9—C10—H10 | 119.5 |
C5—C4—Cl3B | 113.0 (8) | C10—C11—C12 | 122.8 (10) |
Cl1B—C4—Cl3B | 123.5 (8) | C10—C11—H11 | 118.6 |
C5—C4—Cl3A | 116.5 (7) | C12—C11—H11 | 118.6 |
Cl1B—C4—Cl3A | 136.1 (7) | C11—C12—C13 | 116.8 (9) |
Cl3B—C4—Cl3A | 43.0 (5) | C11—C12—C15 | 120.6 (10) |
C5—C4—Cl1A | 115.4 (7) | C13—C12—C15 | 122.6 (11) |
Cl1B—C4—Cl1A | 32.1 (4) | C12—C13—C8 | 121.9 (9) |
Cl3B—C4—Cl1A | 131.0 (7) | C12—C13—H13 | 119.1 |
Cl3A—C4—Cl1A | 115.4 (7) | C8—C13—H13 | 119.1 |
C5—C4—Cl2 | 107.8 (8) | C9—C14—H14A | 109.5 |
Cl1B—C4—Cl2 | 69.8 (7) | C9—C14—H14B | 109.5 |
Cl3B—C4—Cl2 | 61.1 (6) | H14A—C14—H14B | 109.5 |
Cl3A—C4—Cl2 | 101.2 (5) | C9—C14—H14C | 109.5 |
Cl1A—C4—Cl2 | 96.8 (6) | H14A—C14—H14C | 109.5 |
O6—C5—N7 | 124.5 (10) | H14B—C14—H14C | 109.5 |
O6—C5—C4 | 123.3 (12) | C12—C15—H15A | 109.5 |
N7—C5—C4 | 112.1 (10) | C12—C15—H15B | 109.5 |
C9—C8—C13 | 122.6 (9) | H15A—C15—H15B | 109.5 |
C9—C8—N7 | 118.0 (9) | C12—C15—H15C | 109.5 |
C13—C8—N7 | 119.4 (9) | H15A—C15—H15C | 109.5 |
C8—C9—C10 | 114.8 (9) | H15B—C15—H15C | 109.5 |
C8—C9—C14 | 123.7 (9) | ||
C8—N7—C5—O6 | −7.0 (17) | C13—C8—C9—C10 | −0.2 (13) |
C8—N7—C5—C4 | 176.0 (8) | N7—C8—C9—C10 | 178.7 (9) |
Cl1B—C4—C5—O6 | 84.0 (14) | C13—C8—C9—C14 | −178.4 (9) |
Cl3B—C4—C5—O6 | −55.0 (16) | N7—C8—C9—C14 | 0.6 (13) |
Cl3A—C4—C5—O6 | −102.5 (14) | C8—C9—C10—C11 | 0.6 (14) |
Cl1A—C4—C5—O6 | 117.4 (13) | C14—C9—C10—C11 | 178.8 (9) |
Cl2—C4—C5—O6 | 10.4 (14) | C9—C10—C11—C12 | −1.1 (17) |
Cl1B—C4—C5—N7 | −99.0 (10) | C10—C11—C12—C13 | 1.0 (15) |
Cl3B—C4—C5—N7 | 121.9 (10) | C10—C11—C12—C15 | 179.7 (10) |
Cl3A—C4—C5—N7 | 74.5 (11) | C11—C12—C13—C8 | −0.6 (14) |
Cl1A—C4—C5—N7 | −65.6 (11) | C15—C12—C13—C8 | −179.3 (9) |
Cl2—C4—C5—N7 | −172.6 (7) | C9—C8—C13—C12 | 0.3 (14) |
C5—N7—C8—C9 | −127.3 (10) | N7—C8—C13—C12 | −178.7 (9) |
C5—N7—C8—C13 | 51.7 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7N···O6i | 0.86 | 2.12 | 2.984 (11) | 178 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C10H10Cl3NO |
Mr | 266.54 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 299 |
a, b, c (Å) | 4.9173 (9), 11.290 (1), 21.070 (2) |
V (Å3) | 1169.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.16 × 0.12 × 0.06 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.889, 0.956 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6121, 2314, 703 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.088, 0.309, 0.86 |
No. of reflections | 2314 |
No. of parameters | 154 |
No. of restraints | 37 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.76 |
Absolute structure | Flack (1983), 887 Friedel pairs |
Absolute structure parameter | −0.4 (4) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7N···O6i | 0.86 | 2.12 | 2.984 (11) | 177.9 |
Symmetry code: (i) x+1, y, z. |
Acknowledgements
BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.
References
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2343–o2344. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007). Acta Cryst. E63, o2571–o2572. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2004). CrysAlis CCD. Oxford Diffraction Ltd. Köln, Germany. Google Scholar
Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd. Köln, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shilpa & Gowda, B. T. (2007). Z. Naturforsch. Teil A, 62, 84–90. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
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In the present work, the structure of 2,2,2-trichloro-N- (2,5-dimethylphenyl)acetamide (25DMPTCA) has been determined to study the effect of substituents on the structures of N-aromatic amides (Gowda, Foro et al., 2007; Gowda, Kožíšek et al., 2007). The conformation of the N—H bond in 25DMPTCA is syn to the 2-methyl and anti to the 5-methyl substituents in the aromatic ring (Fig. 1), similar to the syn conformation observed with respect to the 2-methyl substituent in 2,2,2-trichloro-N-(2-methylphenyl)acetamide (2MPTCA) (Gowda, Kožíšek et al., 2007). The bond parameters in 25DMPTCA are similar to those in 2MPTCA, 2,2,2-trichloro-N-(2,6-dimethylphenyl)- acetamide and other acetanilides (Gowda, Foro et al., 2007; Gowda, Kožíšek et al., 2007). The intermolecular N—H···O hydrogen bonds link the molecules into chains (Table 1 and Fig.2). The Cl atoms of CCl3 group are disordered and Cl1 and Cl3 were refined using a split model with site-occupation factors 0.5:0.5. No reliable disorder model could be produced for Cl2.