2-(4-Bromo­phen­yl)-N-(2,6-dimethyl­phen­yl)acetamide

Fun, H.-K.; Quah, C.K.; Nayak, P.S.; Narayana, B.; Sarojini, B.K.

doi:10.1107/S1600536812034617

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2678

doi:10.1107/S1600536812034617

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2-(4-Bromophenyl)-N-(2,6-dimethylphenyl)acetamide

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Prakash S. Nayak,^b B. Narayana ^b and B. K. Sarojini ^c

^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

(Received 31 July 2012; accepted 3 August 2012; online 11 August 2012)

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

C₁₆H₁₆BrNO
M_r = 318.21
Monoclinic, P 2₁ /c
a = 4.7146 (6) Å
b = 22.999 (3) Å
c = 13.5350 (15) Å
β = 91.138 (3)°
V = 1467.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.79 mm⁻¹
T = 296 K
0.18 × 0.09 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.635, T_max = 0.822
14048 measured reflections
3352 independent reflections
1593 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.143
S = 1.01
3352 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: APEX2 (Bruker, 2009); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812034617/hb6926sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034617/hb6926Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812034617/hb6926Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

2-(4-Bromophenyl)-N-(2,6-dimethylphenyl)acetamide top

Crystal data top

C₁₆H₁₆BrNO	F(000) = 648
M_r = 318.21	D_x = 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

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	3352 independent reflections
Radiation source: fine-focus sealed tube	1593 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.635, T_max = 0.822	k = −26→29
14048 measured reflections	l = −17→17

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)] = 0.052	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(F_o²) + (0.0518P)² + 0.539P] where P = (F_o² + 2F_c²)/3
3352 reflections	(Δ/σ)_max = 0.001
178 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₁₆H₁₆BrNO	V = 1467.3 (3) Å³
M_r = 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)°

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	3352 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1593 reflections with I > 2σ(I)
T_min = 0.635, T_max = 0.822	R_int = 0.074
14048 measured reflections

Refinement top

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	Δρ_max = 0.37 e Å⁻³
3352 reflections	Δρ_min = −0.57 e Å⁻³
178 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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.635, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	14048, 3352, 1593
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.57

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

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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