2-(4-Bromophenyl)-2-methyl­propan­amide

Wang, J.; Li, H.; Sun, H.

doi:10.1107/S1600536810009657

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o925

doi:10.1107/S1600536810009657

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2-(4-Bromophenyl)-2-methylpropanamide

Jian Wang,^a ^* Hui Li ^a and Hong Sun ^a

^aDepartment of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, People's Republic of China
^*Correspondence e-mail: wangjian_tju@126.com

(Received 12 March 2010; accepted 15 March 2010; online 27 March 2010)

In the crystal of the title compound, C₁₀H₁₂BrNO, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(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 ).

Experimental

Crystal data

C₁₀H₁₂BrNO
M_r = 242.12
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.074
S = 0.99
1787 reflections
128 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.89 (1)	2.12 (1)	2.990 (3)	167 (3)
N1—H1B⋯O1ⁱⁱ	0.88 (1)	2.12 (1)	3.002 (3)	173 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+2.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku/MSC, 2005).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: CrystalStructure (Rigaku/MSC, 2005).

Figures top

	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).

2-(4-Bromophenyl)-2-methylpropanamide top

Crystal data top

C₁₀H₁₂BrNO	F(000) = 488
M_r = 242.12	D_x = 1.586 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3466 reflections
a = 16.425 (8) Å	θ = 2.2–27.9°
b = 6.135 (3) Å	µ = 4.01 mm⁻¹
c = 10.152 (5) Å	T = 113 K
β = 97.613 (7)°	Prism, colourless
V = 1013.9 (8) Å³	0.20 × 0.18 × 0.12 mm
Z = 4

Data collection top

Rigaku Saturn CCD diffractometer	1787 independent reflections
Radiation source: rotating anode	1333 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.090
Detector resolution: 14.63 pixels mm^-1	θ_max = 25.0°, θ_min = 2.5°
ω and ϕ scans	h = −19→19
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −7→7
T_min = 0.501, T_max = 0.644	l = −12→12
9829 measured reflections

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0242P)²] where P = (F_o² + 2F_c²)/3
1787 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.55 e Å⁻³
3 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

C₁₀H₁₂BrNO	V = 1013.9 (8) Å³
M_r = 242.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.425 (8) Å	µ = 4.01 mm⁻¹
b = 6.135 (3) Å	T = 113 K
c = 10.152 (5) Å	0.20 × 0.18 × 0.12 mm
β = 97.613 (7)°

Data collection top

Rigaku Saturn CCD diffractometer	1787 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1333 reflections with I > 2σ(I)
T_min = 0.501, T_max = 0.644	R_int = 0.090
9829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.55 e Å⁻³
1787 reflections	Δρ_min = −0.53 e Å⁻³
128 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.44964 (2)	0.60527 (5)	0.82615 (4)	0.03800 (16)
O1	0.07026 (12)	0.3192 (3)	1.10663 (18)	0.0161 (5)
N1	0.05185 (16)	0.3190 (4)	0.8836 (2)	0.0152 (6)
C1	0.25495 (19)	0.4020 (4)	1.0149 (3)	0.0172 (7)
H1	0.2230	0.4624	1.0773	0.021*
C2	0.3202 (2)	0.5183 (5)	0.9799 (3)	0.0211 (7)
H2	0.3331	0.6576	1.0180	0.025*
C3	0.36720 (19)	0.4317 (5)	0.8887 (3)	0.0207 (7)
C4	0.35071 (19)	0.2238 (5)	0.8383 (3)	0.0241 (8)
H4	0.3844	0.1611	0.7792	0.029*
C5	0.28481 (19)	0.1088 (5)	0.8747 (3)	0.0178 (7)
H5	0.2737	−0.0335	0.8400	0.021*
C6	0.23442 (18)	0.1968 (4)	0.9608 (3)	0.0124 (6)
C7	0.15824 (18)	0.0770 (4)	0.9971 (3)	0.0122 (7)
C8	0.12810 (19)	−0.1034 (4)	0.8969 (3)	0.0170 (7)
H8A	0.1223	−0.0439	0.8066	0.026*
H8B	0.0748	−0.1582	0.9159	0.026*
H8C	0.1680	−0.2230	0.9044	0.026*
C9	0.17838 (19)	−0.0249 (4)	1.1358 (3)	0.0168 (7)
H9A	0.2222	−0.1331	1.1346	0.025*
H9B	0.1292	−0.0960	1.1608	0.025*
H9C	0.1966	0.0893	1.2005	0.025*
C10	0.08953 (17)	0.2487 (4)	1.0001 (3)	0.0117 (6)
H1A	0.0657 (16)	0.283 (4)	0.8050 (15)	0.025 (9)*
H1B	0.0127 (13)	0.417 (4)	0.885 (2)	0.025 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0253 (3)	0.0389 (3)	0.0549 (3)	−0.00663 (17)	0.0241 (2)	0.00685 (18)
O1	0.0196 (13)	0.0189 (11)	0.0122 (11)	0.0030 (9)	0.0113 (9)	−0.0008 (9)
N1	0.0169 (15)	0.0182 (14)	0.0121 (14)	0.0065 (12)	0.0079 (12)	−0.0018 (11)
C1	0.0176 (19)	0.0195 (17)	0.0161 (16)	0.0028 (14)	0.0078 (14)	0.0009 (13)
C2	0.0189 (19)	0.0212 (17)	0.0237 (18)	0.0021 (14)	0.0049 (15)	0.0023 (14)
C3	0.0107 (18)	0.0303 (19)	0.0229 (18)	−0.0003 (14)	0.0089 (14)	0.0090 (14)
C4	0.0163 (19)	0.0298 (19)	0.0294 (19)	0.0059 (15)	0.0151 (15)	0.0007 (15)
C5	0.0183 (19)	0.0183 (17)	0.0190 (17)	0.0011 (13)	0.0103 (14)	0.0003 (13)
C6	0.0131 (17)	0.0135 (15)	0.0115 (15)	0.0032 (13)	0.0047 (13)	0.0026 (12)
C7	0.0147 (18)	0.0117 (15)	0.0119 (15)	0.0027 (12)	0.0079 (13)	−0.0001 (12)
C8	0.0187 (19)	0.0152 (16)	0.0189 (17)	0.0012 (13)	0.0084 (14)	−0.0001 (13)
C9	0.021 (2)	0.0164 (16)	0.0146 (16)	0.0014 (14)	0.0087 (14)	0.0013 (13)
C10	0.0117 (16)	0.0101 (15)	0.0154 (16)	−0.0049 (12)	0.0090 (14)	0.0009 (13)

Geometric parameters (Å, º) top

Br1—C3	1.897 (3)	C5—C6	1.391 (4)
O1—C10	1.245 (3)	C5—H5	0.9500
N1—C10	1.332 (3)	C6—C7	1.537 (4)
N1—H1A	0.886 (9)	C7—C9	1.536 (4)
N1—H1B	0.882 (9)	C7—C8	1.540 (4)
C1—C2	1.373 (4)	C7—C10	1.547 (4)
C1—C6	1.396 (4)	C8—H8A	0.9800
C1—H1	0.9500	C8—H8B	0.9800
C2—C3	1.387 (4)	C8—H8C	0.9800
C2—H2	0.9500	C9—H9A	0.9800
C3—C4	1.387 (4)	C9—H9B	0.9800
C4—C5	1.383 (4)	C9—H9C	0.9800
C4—H4	0.9500

C10—N1—H1A	125.1 (16)	C9—C7—C6	109.3 (2)
C10—N1—H1B	117.5 (15)	C9—C7—C8	108.9 (2)
H1A—N1—H1B	117.2 (16)	C6—C7—C8	112.7 (2)
C2—C1—C6	121.5 (3)	C9—C7—C10	109.2 (2)
C2—C1—H1	119.2	C6—C7—C10	107.4 (2)
C6—C1—H1	119.2	C8—C7—C10	109.3 (2)
C1—C2—C3	119.7 (3)	C7—C8—H8A	109.5
C1—C2—H2	120.1	C7—C8—H8B	109.5
C3—C2—H2	120.1	H8A—C8—H8B	109.5
C4—C3—C2	120.0 (3)	C7—C8—H8C	109.5
C4—C3—Br1	120.3 (2)	H8A—C8—H8C	109.5
C2—C3—Br1	119.6 (2)	H8B—C8—H8C	109.5
C5—C4—C3	119.5 (3)	C7—C9—H9A	109.5
C5—C4—H4	120.3	C7—C9—H9B	109.5
C3—C4—H4	120.3	H9A—C9—H9B	109.5
C4—C5—C6	121.5 (3)	C7—C9—H9C	109.5
C4—C5—H5	119.3	H9A—C9—H9C	109.5
C6—C5—H5	119.3	H9B—C9—H9C	109.5
C5—C6—C1	117.7 (3)	O1—C10—N1	121.1 (3)
C5—C6—C7	122.4 (3)	O1—C10—C7	121.6 (2)
C1—C6—C7	119.9 (3)	N1—C10—C7	117.3 (2)

C6—C1—C2—C3	0.0 (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—Br1	173.2 (2)	C1—C6—C7—C8	160.7 (2)
C2—C3—C4—C5	3.1 (5)	C5—C6—C7—C10	−139.6 (3)
Br1—C3—C4—C5	−173.2 (2)	C1—C6—C7—C10	40.3 (3)
C3—C4—C5—C6	0.1 (5)	C9—C7—C10—O1	14.6 (4)
C4—C5—C6—C1	−3.1 (4)	C6—C7—C10—O1	−103.8 (3)
C4—C5—C6—C7	176.8 (3)	C8—C7—C10—O1	133.6 (3)
C2—C1—C6—C5	3.0 (4)	C9—C7—C10—N1	−165.7 (2)
C2—C1—C6—C7	−176.8 (3)	C6—C7—C10—N1	75.9 (3)
C5—C6—C7—C9	102.1 (3)	C8—C7—C10—N1	−46.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.89 (1)	2.12 (1)	2.990 (3)	167 (3)
N1—H1B···O1ⁱⁱ	0.88 (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.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂BrNO
M_r	242.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	16.425 (8), 6.135 (3), 10.152 (5)
β (°)	97.613 (7)
V (Å³)	1013.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.01
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.501, 0.644
No. of measured, independent and observed [I > 2σ(I)] reflections	9829, 1787, 1333
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.074, 0.99
No. of reflections	1787
No. of parameters	128
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.53

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.886 (9)	2.120 (12)	2.990 (3)	167 (3)
N1—H1B···O1ⁱⁱ	0.882 (9)	2.124 (10)	3.002 (3)	173 (3)

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

Acknowledgements

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

References

Koltunov, K. Y., Walspurger, S. & Sommer, J. (2004). Eur. J. Org. Chem. pp. 4039–4047. Web of Science CrossRef Google Scholar
Rigaku/MSC (2005). CrystalClear and CrystalStructure. 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