organic compounds
2-(4-Bromophenyl)-N-(2,6-dimethylphenyl)acetamide
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and cDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India
*Correspondence e-mail: hkfun@usm.my
In the title compound, C16H16BrNO, the dihedral angle between the benzene rings is 69.8 (2)°. In the crystal, N—H⋯O hydrogen bonds link the molecules into C(4) chains propagating in [100]. Adjacent molecules in the chains are also linked by C—H⋯O interactions which, along with the N—H⋯O hydrogen bonds, generate R21(6) loops.
Related literature
For general background to the title compound and for related structures, see: Fun et al. (2011a,b, 2012a,b). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812034617/hb6926sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812034617/hb6926Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812034617/hb6926Isup3.cml
4-Bromophenylacetic acid (0.213 g, 1 mmol), 2,6-Dimethylaniline (0.1 ml, 1 mmol) and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (1.0 g, 0.01 mol) were dissolved in dichloromethane (20 ml). The mixture was stirred in presence of triethylamine at 273 K for about 3 h. The contents were poured into 100 ml of ice-cold aqueous hydrochloric acid with stirring. The resulting solution was extracted thrice with dichloromethane. The organic layer was washed with saturated NaHCO3 solution and brine solution, dried and concentrated under reduced pressure to give the title compound (I). Colourless plates were grown from a methanol and N,N-dimethylformamide (1:1) solvent mixture by the slow evaporation method (m.p.:479-481 K).
Atom H1N1 was located in a difference Fourier map and refined freely [N–H = 0.91 (4) Å]. The remaining H atoms were positioned geometrically and refined using a riding model with C–H = 0.93-0.97 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating-group model was applied for the methyl groups.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C16H16BrNO | F(000) = 648 |
Mr = 318.21 | Dx = 1.440 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1376 reflections |
a = 4.7146 (6) Å | θ = 3.0–20.1° |
b = 22.999 (3) Å | µ = 2.79 mm−1 |
c = 13.5350 (15) Å | T = 296 K |
β = 91.138 (3)° | Plate, colourless |
V = 1467.3 (3) Å3 | 0.18 × 0.09 × 0.07 mm |
Z = 4 |
Bruker SMART APEXII DUO CCD diffractometer | 3352 independent reflections |
Radiation source: fine-focus sealed tube | 1593 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −6→6 |
Tmin = 0.635, Tmax = 0.822 | k = −26→29 |
14048 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0518P)2 + 0.539P] where P = (Fo2 + 2Fc2)/3 |
3352 reflections | (Δ/σ)max = 0.001 |
178 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
C16H16BrNO | V = 1467.3 (3) Å3 |
Mr = 318.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.7146 (6) Å | µ = 2.79 mm−1 |
b = 22.999 (3) Å | T = 296 K |
c = 13.5350 (15) Å | 0.18 × 0.09 × 0.07 mm |
β = 91.138 (3)° |
Bruker SMART APEXII DUO CCD diffractometer | 3352 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1593 reflections with I > 2σ(I) |
Tmin = 0.635, Tmax = 0.822 | Rint = 0.074 |
14048 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.37 e Å−3 |
3352 reflections | Δρmin = −0.57 e Å−3 |
178 parameters |
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 | ||
Br1 | 0.41005 (16) | 0.35233 (3) | 0.61576 (4) | 0.1038 (3) | |
O1 | 0.4016 (5) | 0.33510 (13) | 1.1247 (2) | 0.0615 (8) | |
N1 | −0.0290 (7) | 0.37234 (13) | 1.1589 (2) | 0.0416 (7) | |
C1 | 0.0074 (10) | 0.35773 (19) | 0.8830 (4) | 0.0688 (13) | |
H1A | −0.1203 | 0.3825 | 0.9134 | 0.083* | |
C2 | 0.0970 (11) | 0.3706 (2) | 0.7894 (4) | 0.0744 (14) | |
H2A | 0.0300 | 0.4037 | 0.7570 | 0.089* | |
C3 | 0.2837 (10) | 0.33480 (19) | 0.7448 (3) | 0.0614 (11) | |
C4 | 0.3828 (10) | 0.28624 (19) | 0.7918 (3) | 0.0652 (12) | |
H4A | 0.5100 | 0.2616 | 0.7609 | 0.078* | |
C5 | 0.2916 (9) | 0.27413 (17) | 0.8861 (3) | 0.0550 (10) | |
H5A | 0.3608 | 0.2413 | 0.9186 | 0.066* | |
C6 | 0.1019 (8) | 0.30930 (17) | 0.9327 (3) | 0.0469 (9) | |
C7 | 0.0048 (8) | 0.29567 (17) | 1.0356 (3) | 0.0531 (10) | |
H7A | 0.0515 | 0.2557 | 1.0517 | 0.064* | |
H7B | −0.1996 | 0.3000 | 1.0383 | 0.064* | |
C8 | 0.1443 (8) | 0.33567 (16) | 1.1105 (3) | 0.0464 (9) | |
C9 | 0.0737 (7) | 0.41182 (15) | 1.2329 (2) | 0.0380 (8) | |
C10 | 0.2465 (8) | 0.45805 (16) | 1.2062 (3) | 0.0477 (9) | |
C11 | 0.3468 (10) | 0.49491 (18) | 1.2805 (3) | 0.0664 (12) | |
H11A | 0.4670 | 0.5254 | 1.2645 | 0.080* | |
C12 | 0.2719 (10) | 0.4871 (2) | 1.3765 (3) | 0.0704 (13) | |
H12A | 0.3412 | 0.5122 | 1.4251 | 0.084* | |
C13 | 0.0963 (10) | 0.4428 (2) | 1.4010 (3) | 0.0618 (12) | |
H13A | 0.0450 | 0.4383 | 1.4666 | 0.074* | |
C14 | −0.0091 (8) | 0.40372 (16) | 1.3301 (3) | 0.0470 (9) | |
C15 | 0.3245 (11) | 0.4697 (2) | 1.1008 (3) | 0.0736 (13) | |
H15A | 0.1636 | 0.4621 | 1.0581 | 0.110* | |
H15B | 0.4787 | 0.4448 | 1.0829 | 0.110* | |
H15C | 0.3808 | 0.5096 | 1.0941 | 0.110* | |
C16 | −0.2007 (10) | 0.35451 (19) | 1.3576 (3) | 0.0680 (12) | |
H16A | −0.1351 | 0.3192 | 1.3278 | 0.102* | |
H16B | −0.3903 | 0.3627 | 1.3344 | 0.102* | |
H16C | −0.1992 | 0.3502 | 1.4281 | 0.102* | |
H1N1 | −0.220 (8) | 0.3663 (14) | 1.153 (3) | 0.042 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.1668 (7) | 0.0908 (4) | 0.0537 (3) | −0.0423 (4) | 0.0020 (3) | 0.0035 (3) |
O1 | 0.0288 (15) | 0.081 (2) | 0.0748 (19) | 0.0040 (14) | 0.0040 (14) | −0.0234 (15) |
N1 | 0.0260 (17) | 0.0529 (19) | 0.0457 (17) | 0.0002 (15) | −0.0001 (15) | −0.0070 (14) |
C1 | 0.063 (3) | 0.064 (3) | 0.079 (3) | 0.022 (2) | −0.002 (3) | −0.012 (3) |
C2 | 0.085 (4) | 0.061 (3) | 0.076 (3) | 0.013 (3) | −0.014 (3) | 0.008 (2) |
C3 | 0.077 (3) | 0.055 (3) | 0.052 (2) | −0.015 (2) | −0.003 (2) | −0.005 (2) |
C4 | 0.083 (3) | 0.056 (3) | 0.057 (3) | 0.007 (2) | 0.015 (3) | −0.011 (2) |
C5 | 0.064 (3) | 0.047 (2) | 0.053 (2) | 0.010 (2) | 0.005 (2) | −0.0060 (18) |
C6 | 0.038 (2) | 0.050 (2) | 0.053 (2) | −0.0018 (19) | −0.0050 (19) | −0.0126 (19) |
C7 | 0.036 (2) | 0.062 (3) | 0.061 (2) | −0.0096 (19) | 0.010 (2) | −0.021 (2) |
C8 | 0.033 (2) | 0.057 (2) | 0.050 (2) | 0.0006 (19) | 0.0076 (19) | −0.0070 (18) |
C9 | 0.0304 (19) | 0.041 (2) | 0.0421 (19) | 0.0044 (16) | −0.0021 (17) | −0.0023 (16) |
C10 | 0.047 (2) | 0.044 (2) | 0.052 (2) | 0.0030 (19) | −0.0013 (19) | 0.0040 (18) |
C11 | 0.067 (3) | 0.052 (3) | 0.079 (3) | −0.009 (2) | −0.005 (3) | −0.010 (2) |
C12 | 0.079 (3) | 0.066 (3) | 0.066 (3) | 0.000 (3) | −0.011 (3) | −0.024 (2) |
C13 | 0.071 (3) | 0.074 (3) | 0.040 (2) | 0.016 (3) | 0.000 (2) | −0.010 (2) |
C14 | 0.042 (2) | 0.052 (2) | 0.048 (2) | 0.0086 (19) | 0.0069 (19) | 0.0016 (18) |
C15 | 0.090 (4) | 0.069 (3) | 0.062 (3) | −0.014 (3) | 0.006 (3) | 0.019 (2) |
C16 | 0.061 (3) | 0.084 (3) | 0.059 (3) | 0.002 (3) | 0.017 (2) | 0.010 (2) |
Br1—C3 | 1.899 (4) | C7—H7B | 0.9700 |
O1—C8 | 1.224 (4) | C9—C10 | 1.392 (5) |
N1—C8 | 1.353 (5) | C9—C14 | 1.392 (5) |
N1—C9 | 1.429 (4) | C10—C11 | 1.391 (5) |
N1—H1N1 | 0.91 (4) | C10—C15 | 1.504 (5) |
C1—C6 | 1.371 (6) | C11—C12 | 1.365 (6) |
C1—C2 | 1.376 (6) | C11—H11A | 0.9300 |
C1—H1A | 0.9300 | C12—C13 | 1.358 (6) |
C2—C3 | 1.356 (6) | C12—H12A | 0.9300 |
C2—H2A | 0.9300 | C13—C14 | 1.400 (5) |
C3—C4 | 1.363 (6) | C13—H13A | 0.9300 |
C4—C5 | 1.383 (5) | C14—C16 | 1.500 (5) |
C4—H4A | 0.9300 | C15—H15A | 0.9600 |
C5—C6 | 1.369 (5) | C15—H15B | 0.9600 |
C5—H5A | 0.9300 | C15—H15C | 0.9600 |
C6—C7 | 1.508 (5) | C16—H16A | 0.9600 |
C7—C8 | 1.510 (5) | C16—H16B | 0.9600 |
C7—H7A | 0.9700 | C16—H16C | 0.9600 |
C8—N1—C9 | 122.4 (3) | C10—C9—C14 | 121.6 (3) |
C8—N1—H1N1 | 118 (2) | C10—C9—N1 | 119.7 (3) |
C9—N1—H1N1 | 118 (2) | C14—C9—N1 | 118.7 (3) |
C6—C1—C2 | 121.6 (4) | C11—C10—C9 | 118.0 (4) |
C6—C1—H1A | 119.2 | C11—C10—C15 | 119.4 (4) |
C2—C1—H1A | 119.2 | C9—C10—C15 | 122.6 (4) |
C3—C2—C1 | 119.5 (4) | C12—C11—C10 | 121.2 (4) |
C3—C2—H2A | 120.2 | C12—C11—H11A | 119.4 |
C1—C2—H2A | 120.2 | C10—C11—H11A | 119.4 |
C2—C3—C4 | 120.6 (4) | C13—C12—C11 | 120.2 (4) |
C2—C3—Br1 | 119.9 (4) | C13—C12—H12A | 119.9 |
C4—C3—Br1 | 119.5 (3) | C11—C12—H12A | 119.9 |
C3—C4—C5 | 119.1 (4) | C12—C13—C14 | 121.6 (4) |
C3—C4—H4A | 120.5 | C12—C13—H13A | 119.2 |
C5—C4—H4A | 120.5 | C14—C13—H13A | 119.2 |
C6—C5—C4 | 121.6 (4) | C9—C14—C13 | 117.4 (4) |
C6—C5—H5A | 119.2 | C9—C14—C16 | 121.2 (3) |
C4—C5—H5A | 119.2 | C13—C14—C16 | 121.4 (4) |
C5—C6—C1 | 117.6 (4) | C10—C15—H15A | 109.5 |
C5—C6—C7 | 121.0 (4) | C10—C15—H15B | 109.5 |
C1—C6—C7 | 121.3 (4) | H15A—C15—H15B | 109.5 |
C6—C7—C8 | 110.9 (3) | C10—C15—H15C | 109.5 |
C6—C7—H7A | 109.5 | H15A—C15—H15C | 109.5 |
C8—C7—H7A | 109.5 | H15B—C15—H15C | 109.5 |
C6—C7—H7B | 109.5 | C14—C16—H16A | 109.5 |
C8—C7—H7B | 109.5 | C14—C16—H16B | 109.5 |
H7A—C7—H7B | 108.0 | H16A—C16—H16B | 109.5 |
O1—C8—N1 | 122.4 (3) | C14—C16—H16C | 109.5 |
O1—C8—C7 | 121.1 (3) | H16A—C16—H16C | 109.5 |
N1—C8—C7 | 116.5 (3) | H16B—C16—H16C | 109.5 |
C6—C1—C2—C3 | −0.1 (7) | C8—N1—C9—C10 | 67.8 (5) |
C1—C2—C3—C4 | 0.1 (7) | C8—N1—C9—C14 | −113.9 (4) |
C1—C2—C3—Br1 | −179.7 (3) | C14—C9—C10—C11 | 3.0 (5) |
C2—C3—C4—C5 | −0.4 (7) | N1—C9—C10—C11 | −178.8 (3) |
Br1—C3—C4—C5 | 179.4 (3) | C14—C9—C10—C15 | −176.3 (4) |
C3—C4—C5—C6 | 0.8 (7) | N1—C9—C10—C15 | 2.0 (5) |
C4—C5—C6—C1 | −0.9 (6) | C9—C10—C11—C12 | −1.8 (6) |
C4—C5—C6—C7 | −179.8 (4) | C15—C10—C11—C12 | 177.4 (4) |
C2—C1—C6—C5 | 0.5 (6) | C10—C11—C12—C13 | 0.0 (7) |
C2—C1—C6—C7 | 179.5 (4) | C11—C12—C13—C14 | 0.9 (7) |
C5—C6—C7—C8 | 104.8 (4) | C10—C9—C14—C13 | −2.2 (5) |
C1—C6—C7—C8 | −74.1 (5) | N1—C9—C14—C13 | 179.6 (3) |
C9—N1—C8—O1 | −2.2 (6) | C10—C9—C14—C16 | 178.6 (4) |
C9—N1—C8—C7 | 178.9 (3) | N1—C9—C14—C16 | 0.3 (5) |
C6—C7—C8—O1 | −63.7 (5) | C12—C13—C14—C9 | 0.2 (6) |
C6—C7—C8—N1 | 115.2 (4) | C12—C13—C14—C16 | 179.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1i | 0.91 (4) | 1.95 (4) | 2.847 (4) | 166 (3) |
C7—H7B···O1i | 0.97 | 2.38 | 3.240 (5) | 148 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H16BrNO |
Mr | 318.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 4.7146 (6), 22.999 (3), 13.5350 (15) |
β (°) | 91.138 (3) |
V (Å3) | 1467.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.79 |
Crystal size (mm) | 0.18 × 0.09 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART APEXII DUO CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.635, 0.822 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14048, 3352, 1593 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.143, 1.01 |
No. of reflections | 3352 |
No. of parameters | 178 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.57 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1i | 0.91 (4) | 1.95 (4) | 2.847 (4) | 166 (3) |
C7—H7B···O1i | 0.97 | 2.38 | 3.240 (5) | 148 |
Symmetry code: (i) x−1, y, z. |
Acknowledgements
The authors would like to thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). BN also thanks the UGC, New Delhi, and the Government of India for the purchase of chemicals through the SAP–DRS-Phase 1 programme.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In continuation of our work on synthesis of amides (Fun et al., 2011a, 2011b, 2012a, 2012b), we report herein the crystal structure of the title compound.
In the title molecule (Fig. 1), the two benzene rings (C1-C6 and C9-C14) make a dihedral angle of 69.8 (2)°. Bond lengths and angles are within normal ranges and are comparable to related structures (Fun et al., 2011a, 2011b, 2012a, 2012b).
In the crystal structure, Fig. 2, molecules are linked via N1–H1N1···O1 and C7–H7B···O1 hydrogen bonds (Table 1) into one-dimensional [100] chains which contain R21 (6) ring motifs (Bernstein et al., 1995).