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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o925.
Published online 2010 March 27. doi:  10.1107/S1600536810009657
PMCID: PMC2983968

2-(4-Bromophenyl)-2-methyl­propan­amide

Abstract

In the crystal of the title compound, C10H12BrNO, inversion dimers linked by pairs of N—H(...)O hydrogen bonds generate R 2 2(8) loops. Further N—H(...)O hydrogen bonds link the dimers into sheets propagating in (100).

Related literature

For the sythesis, see: Koltunov et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o925-scheme1.jpg

Experimental

Crystal data

  • C10H12BrNO
  • M r = 242.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o925-efi1.jpg
  • a = 16.425 (8) Å
  • b = 6.135 (3) Å
  • c = 10.152 (5) Å
  • β = 97.613 (7)°
  • V = 1013.9 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.01 mm−1
  • T = 113 K
  • 0.20 × 0.18 × 0.12 mm

Data collection

  • Rigaku Saturn CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.501, T max = 0.644
  • 9829 measured reflections
  • 1787 independent reflections
  • 1333 reflections with I > 2σ(I)
  • R int = 0.090

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.074
  • S = 0.99
  • 1787 reflections
  • 128 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.55 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009657/hb5360sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009657/hb5360Isup2.hkl

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

Acknowledgments

We thank the College Research Program of Yuncheng University (2008113) for funding.

supplementary crystallographic information

Comment

The reaction of amides towards weak nucleophiles such as nonactivated arenes have very broad utility in organic chemistry. However, little work has been done to investigate it. The title compound was synthesized by a facile method through the reaction of methacrylamide and benzene, catalyzed by AlCl3. In the crystal, the molecules are linked by intermolecular N—H···O hydrogen bonding interactions. Single-crystal X-ray diffraction analysis reveals that the title compound crystallizes in the Monoclinic space group P 21/c.

Experimental

A mixture of AlCl3 (0.95 g, 7.1 mmol) and methacrylamide (0.2 g, 2.3 mmol) in benzene (3 ml) was stirred at 25 °C for 3 h, and was then poured over several grams of ice and extracted with CH2Cl2. The organic phase was separated, dried with anhydrous Na2SO4 and concentrated in vacuo to give a solid mixture of 2-methyl-3-phenylpropionamide and 2-methyl-2-phenylpropionamide (0.41 g, 97%) in 2:1 ratio. The title compound was separated by flash column chromatography on silica gel. Colourless prisms of (I) were obtained by recrystallisation from ethanol.

Refinement

The H atoms were positioned geometrically (C—H=0.95Å or 0.98 Å, N—H=0.88 Å) and refined as riding with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radius.
Fig. 2.
The crystal packing for (I).

Crystal data

C10H12BrNOF(000) = 488
Mr = 242.12Dx = 1.586 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3466 reflections
a = 16.425 (8) Åθ = 2.2–27.9°
b = 6.135 (3) ŵ = 4.01 mm1
c = 10.152 (5) ÅT = 113 K
β = 97.613 (7)°Prism, colourless
V = 1013.9 (8) Å30.20 × 0.18 × 0.12 mm
Z = 4

Data collection

Rigaku Saturn CCD diffractometer1787 independent reflections
Radiation source: rotating anode1333 reflections with I > 2σ(I)
multilayerRint = 0.090
Detector resolution: 14.63 pixels mm-1θmax = 25.0°, θmin = 2.5°
ω and [var phi] scansh = −19→19
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −7→7
Tmin = 0.501, Tmax = 0.644l = −12→12
9829 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 0.99w = 1/[σ2(Fo2) + (0.0242P)2] where P = (Fo2 + 2Fc2)/3
1787 reflections(Δ/σ)max = 0.001
128 parametersΔρmax = 0.55 e Å3
3 restraintsΔρmin = −0.53 e Å3

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 > 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)

xyzUiso*/Ueq
Br10.44964 (2)0.60527 (5)0.82615 (4)0.03800 (16)
O10.07026 (12)0.3192 (3)1.10663 (18)0.0161 (5)
N10.05185 (16)0.3190 (4)0.8836 (2)0.0152 (6)
C10.25495 (19)0.4020 (4)1.0149 (3)0.0172 (7)
H10.22300.46241.07730.021*
C20.3202 (2)0.5183 (5)0.9799 (3)0.0211 (7)
H20.33310.65761.01800.025*
C30.36720 (19)0.4317 (5)0.8887 (3)0.0207 (7)
C40.35071 (19)0.2238 (5)0.8383 (3)0.0241 (8)
H40.38440.16110.77920.029*
C50.28481 (19)0.1088 (5)0.8747 (3)0.0178 (7)
H50.2737−0.03350.84000.021*
C60.23442 (18)0.1968 (4)0.9608 (3)0.0124 (6)
C70.15824 (18)0.0770 (4)0.9971 (3)0.0122 (7)
C80.12810 (19)−0.1034 (4)0.8969 (3)0.0170 (7)
H8A0.1223−0.04390.80660.026*
H8B0.0748−0.15820.91590.026*
H8C0.1680−0.22300.90440.026*
C90.17838 (19)−0.0249 (4)1.1358 (3)0.0168 (7)
H9A0.2222−0.13311.13460.025*
H9B0.1292−0.09601.16080.025*
H9C0.19660.08931.20050.025*
C100.08953 (17)0.2487 (4)1.0001 (3)0.0117 (6)
H1A0.0657 (16)0.283 (4)0.8050 (15)0.025 (9)*
H1B0.0127 (13)0.417 (4)0.885 (2)0.025 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0253 (3)0.0389 (3)0.0549 (3)−0.00663 (17)0.0241 (2)0.00685 (18)
O10.0196 (13)0.0189 (11)0.0122 (11)0.0030 (9)0.0113 (9)−0.0008 (9)
N10.0169 (15)0.0182 (14)0.0121 (14)0.0065 (12)0.0079 (12)−0.0018 (11)
C10.0176 (19)0.0195 (17)0.0161 (16)0.0028 (14)0.0078 (14)0.0009 (13)
C20.0189 (19)0.0212 (17)0.0237 (18)0.0021 (14)0.0049 (15)0.0023 (14)
C30.0107 (18)0.0303 (19)0.0229 (18)−0.0003 (14)0.0089 (14)0.0090 (14)
C40.0163 (19)0.0298 (19)0.0294 (19)0.0059 (15)0.0151 (15)0.0007 (15)
C50.0183 (19)0.0183 (17)0.0190 (17)0.0011 (13)0.0103 (14)0.0003 (13)
C60.0131 (17)0.0135 (15)0.0115 (15)0.0032 (13)0.0047 (13)0.0026 (12)
C70.0147 (18)0.0117 (15)0.0119 (15)0.0027 (12)0.0079 (13)−0.0001 (12)
C80.0187 (19)0.0152 (16)0.0189 (17)0.0012 (13)0.0084 (14)−0.0001 (13)
C90.021 (2)0.0164 (16)0.0146 (16)0.0014 (14)0.0087 (14)0.0013 (13)
C100.0117 (16)0.0101 (15)0.0154 (16)−0.0049 (12)0.0090 (14)0.0009 (13)

Geometric parameters (Å, °)

Br1—C31.897 (3)C5—C61.391 (4)
O1—C101.245 (3)C5—H50.9500
N1—C101.332 (3)C6—C71.537 (4)
N1—H1A0.886 (9)C7—C91.536 (4)
N1—H1B0.882 (9)C7—C81.540 (4)
C1—C21.373 (4)C7—C101.547 (4)
C1—C61.396 (4)C8—H8A0.9800
C1—H10.9500C8—H8B0.9800
C2—C31.387 (4)C8—H8C0.9800
C2—H20.9500C9—H9A0.9800
C3—C41.387 (4)C9—H9B0.9800
C4—C51.383 (4)C9—H9C0.9800
C4—H40.9500
C10—N1—H1A125.1 (16)C9—C7—C6109.3 (2)
C10—N1—H1B117.5 (15)C9—C7—C8108.9 (2)
H1A—N1—H1B117.2 (16)C6—C7—C8112.7 (2)
C2—C1—C6121.5 (3)C9—C7—C10109.2 (2)
C2—C1—H1119.2C6—C7—C10107.4 (2)
C6—C1—H1119.2C8—C7—C10109.3 (2)
C1—C2—C3119.7 (3)C7—C8—H8A109.5
C1—C2—H2120.1C7—C8—H8B109.5
C3—C2—H2120.1H8A—C8—H8B109.5
C4—C3—C2120.0 (3)C7—C8—H8C109.5
C4—C3—Br1120.3 (2)H8A—C8—H8C109.5
C2—C3—Br1119.6 (2)H8B—C8—H8C109.5
C5—C4—C3119.5 (3)C7—C9—H9A109.5
C5—C4—H4120.3C7—C9—H9B109.5
C3—C4—H4120.3H9A—C9—H9B109.5
C4—C5—C6121.5 (3)C7—C9—H9C109.5
C4—C5—H5119.3H9A—C9—H9C109.5
C6—C5—H5119.3H9B—C9—H9C109.5
C5—C6—C1117.7 (3)O1—C10—N1121.1 (3)
C5—C6—C7122.4 (3)O1—C10—C7121.6 (2)
C1—C6—C7119.9 (3)N1—C10—C7117.3 (2)
C6—C1—C2—C30.0 (5)C1—C6—C7—C9−78.0 (3)
C1—C2—C3—C4−3.2 (5)C5—C6—C7—C8−19.2 (4)
C1—C2—C3—Br1173.2 (2)C1—C6—C7—C8160.7 (2)
C2—C3—C4—C53.1 (5)C5—C6—C7—C10−139.6 (3)
Br1—C3—C4—C5−173.2 (2)C1—C6—C7—C1040.3 (3)
C3—C4—C5—C60.1 (5)C9—C7—C10—O114.6 (4)
C4—C5—C6—C1−3.1 (4)C6—C7—C10—O1−103.8 (3)
C4—C5—C6—C7176.8 (3)C8—C7—C10—O1133.6 (3)
C2—C1—C6—C53.0 (4)C9—C7—C10—N1−165.7 (2)
C2—C1—C6—C7−176.8 (3)C6—C7—C10—N175.9 (3)
C5—C6—C7—C9102.1 (3)C8—C7—C10—N1−46.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.89 (1)2.12 (1)2.990 (3)167 (3)
N1—H1B···O1ii0.88 (1)2.12 (1)3.002 (3)173 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5360).

References

  • Koltunov, K. Y., Walspurger, S. & Sommer, J. (2004). Eur. J. Org. Chem. pp. 4039–4047.
  • Rigaku/MSC (2005). CrystalClear and CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography