2-Bromo-2-methyl-N-p-tolyl­propanamide

Moreno-Fuquen, R.; Quintero, D.E.; Zuluaga, F.; Kennedy, A.R.; De Almeida Santos, R.H.

doi:10.1107/S1600536811019337

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1543

doi:10.1107/S1600536811019337

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2-Bromo-2-methyl-N-p-tolylpropanamide

Rodolfo Moreno-Fuquen,^a ^* David E. Quintero,^a Fabio Zuluaga,^a Alan R. Kennedy ^b and Regina H. De Almeida Santos ^c

^aDepartamento de Química, Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, ^bWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland, and ^cInstituto de Química de São Carlos, Universidade de São Paulo, USP, São Carlos, SP, Brazil
^*Correspondence e-mail: rodimo26@yahoo.es

(Received 15 May 2011; accepted 21 May 2011; online 28 May 2011)

In the title molecule, C₁₁H₁₄BrNO, there is twist between the mean plane of the amide group and the benzene ring [C(=O)—N—C C torsion angle = −31.2 (5)°]. In the crystal, intermolecular N—H⋯O and weak C—H⋯O hydrogen bonds link molecules into chains along [100]. The methyl group H atoms are disordered over two sets of sites with equal occupancy.

Related literature

For initiators in ATRP processes (polymerization by atom transfer radical), see: Matyjaszewski & Xia (2001 ); Kato et al. (1995 ); Pietrasik & Tsarevsky (2010 ). For a related structure, see: Moreno-Fuquen et al. (2011 ). For hydrogen-bond graph sets, see: Etter (1990 ).

Experimental

Crystal data

C₁₁H₁₄BrNO
M_r = 256.14
Orthorhombic, P b c a
a = 10.0728 (4) Å
b = 11.2577 (4) Å
c = 20.3670 (6) Å
V = 2309.55 (14) Å³
Z = 8
Mo Kα radiation
μ = 3.53 mm⁻¹
T = 123 K
0.25 × 0.12 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.751, T_max = 1.000
10140 measured reflections
2762 independent reflections
1819 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.093
S = 1.06
2762 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (2)	2.13 (2)	2.937 (3)	161 (3)
C1—H1C⋯O1ⁱ	0.98	2.44	3.382 (4)	162
C10—H10⋯O1ⁱ	0.95	2.57	3.321 (4)	137
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis CCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019337/lh5254sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019337/lh5254Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811019337/lh5254Isup3.cml

checkCIF report

Comment top

The ATRP process (polymerization by atom transfer radical) allows control of the composition and functionality in polymerization reactions (Pietrasik & Tsarevsky, 2010). The use of functional initiators in these reactions allows the synthesis of new materials. Most initiators for ATRP processes are alkyl halides (Matyjaszewski & Xia, 2001; Kato et al., 1995). As part of our work related to functional initiators in polymerization processes (Moreno-Fuquen et al., 2011) we have determined the crystal structure of the title compound (I). The molecular structure of (I) is shown in Fig. 1. There is a twist between the mean plane of the amide group and benzene ring giving a C4—N1—C5—C6 torsion angle of -31.2 (5) °. In the crystal, intermolecular N—H···O and weak C—H···O hydrogen bonds link molecules into one-dimensional chains along [100] incorporating C(4) graph motifs (Etter, 1990) (see Table 1 and Fig. 2).

Related literature top

For initiators in ATRP processes (polymerization by atom transfer radical), see: Matyjaszewski & Xia (2001); Kato et al. (1995); Pietrasik & Tsarevsky (2010). For a related structure, see: Moreno-Fuquen et al. (2011). For hydrogen-bond graph sets, see: Etter (1990).

Experimental top

The initial reagents were purchased from Aldrich Chemical Co. and were used as received. In a 100mL round bottom flask 4-methylaniline (3.173 mmoles, 0.340 g), triethylamine (0.635 mmol, 0.064 g) were mixed, then a solution of 2-bromo isobutiryl bromide (0.685 g) in anhydrous THF (5 ml) was added drop wise, under an argon stream. The reaction was carried out in a dry bag overnight under magnetic stirring. The solid was filtered off and dichloromethane (20 ml) added to the organic phase which was washed with brine (50 ml) followed by water (10 ml). The solution was concentrated at low pressure affording colourless crystals and recrystalized from a solution of hexane and ethyl acetate (80:20). M.p. 364 (1) K.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis CCD (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. An ORTEP-3 (Farrugia, 1997) plot of (I) with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a one dimensional chain along [100]. Symmetry code: (i) x-1/2,+y,-z+1/2.

2-Bromo-2-methyl-N-p-tolylpropanamide top

Crystal data top

C₁₁H₁₄BrNO	D_x = 1.473 Mg m⁻³
M_r = 256.14	Melting point: 385(1) K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2266 reflections
a = 10.0728 (4) Å	θ = 3.4–29.5°
b = 11.2577 (4) Å	µ = 3.53 mm⁻¹
c = 20.3670 (6) Å	T = 123 K
V = 2309.55 (14) Å³	Tablet, colourless
Z = 8	0.25 × 0.12 × 0.05 mm
F(000) = 1040

Data collection top

Oxford Diffraction Xcalibur E diffractometer	2762 independent reflections
Radiation source: fine-focus sealed tube	1819 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 28.0°, θ_min = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −12→13
T_min = 0.751, T_max = 1.000	k = −10→14
10140 measured reflections	l = −26→22

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0316P)² + 0.7321P] where P = (F_o² + 2F_c²)/3
2762 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₁H₁₄BrNO	V = 2309.55 (14) Å³
M_r = 256.14	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.0728 (4) Å	µ = 3.53 mm⁻¹
b = 11.2577 (4) Å	T = 123 K
c = 20.3670 (6) Å	0.25 × 0.12 × 0.05 mm

Data collection top

Oxford Diffraction Xcalibur E diffractometer	2762 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1819 reflections with I > 2σ(I)
T_min = 0.751, T_max = 1.000	R_int = 0.049
10140 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.58 e Å⁻³
2762 reflections	Δρ_min = −0.46 e Å⁻³
133 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	Occ. (<1)
Br1	0.74332 (3)	0.28652 (3)	0.384590 (15)	0.02982 (13)
O1	0.94616 (17)	0.2851 (2)	0.24129 (10)	0.0200 (5)
N1	0.7262 (2)	0.2730 (3)	0.21911 (12)	0.0158 (6)
C1	0.6864 (3)	0.4811 (3)	0.30022 (16)	0.0214 (7)
H1A	0.7056	0.5288	0.2611	0.032*
H1B	0.6768	0.5335	0.3384	0.032*
H1C	0.6037	0.4368	0.2935	0.032*
C2	0.7996 (3)	0.3946 (3)	0.31211 (15)	0.0173 (7)
C3	0.9232 (3)	0.4587 (3)	0.33541 (16)	0.0287 (9)
H3A	0.9914	0.4004	0.3472	0.043*
H3B	0.9015	0.5073	0.3739	0.043*
H3C	0.9565	0.5100	0.3002	0.043*
C4	0.8312 (3)	0.3116 (3)	0.25448 (14)	0.0158 (7)
C5	0.7307 (2)	0.1928 (3)	0.16557 (14)	0.0160 (7)
C6	0.8384 (3)	0.1847 (3)	0.12261 (14)	0.0203 (7)
H6	0.9135	0.2348	0.1281	0.024*
C7	0.8347 (3)	0.1030 (3)	0.07213 (15)	0.0241 (8)
H7	0.9082	0.0986	0.0431	0.029*
C8	0.7285 (3)	0.0274 (3)	0.06198 (15)	0.0229 (8)
C9	0.6210 (3)	0.0383 (3)	0.10438 (16)	0.0273 (8)
H9	0.5457	−0.0113	0.0985	0.033*
C10	0.6216 (3)	0.1202 (3)	0.15499 (15)	0.0225 (8)
H10	0.5463	0.1267	0.1829	0.027*
C11	0.7287 (3)	−0.0636 (4)	0.00758 (17)	0.0338 (9)
H11A	0.6452	−0.1082	0.0085	0.051*	0.50
H11B	0.8033	−0.1184	0.0138	0.051*	0.50
H11C	0.7378	−0.0233	−0.0348	0.051*	0.50
H11D	0.8123	−0.0584	−0.0168	0.051*	0.50
H11E	0.6542	−0.0482	−0.0222	0.051*	0.50
H11F	0.7197	−0.1433	0.0264	0.051*	0.50
H1N	0.652 (2)	0.292 (3)	0.2342 (15)	0.032 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0475 (2)	0.0235 (2)	0.01844 (18)	0.00201 (17)	0.00410 (15)	0.00302 (15)
O1	0.0101 (9)	0.0260 (14)	0.0240 (12)	0.0013 (10)	−0.0012 (8)	−0.0053 (11)
N1	0.0086 (12)	0.0198 (15)	0.0191 (13)	0.0006 (11)	0.0013 (9)	−0.0026 (11)
C1	0.0213 (16)	0.017 (2)	0.0254 (18)	0.0021 (13)	0.0028 (14)	−0.0020 (15)
C2	0.0131 (13)	0.0159 (19)	0.0228 (17)	−0.0020 (12)	0.0012 (12)	0.0001 (15)
C3	0.0218 (16)	0.037 (3)	0.0269 (19)	−0.0069 (16)	−0.0011 (14)	−0.0152 (18)
C4	0.0163 (14)	0.0137 (18)	0.0175 (15)	−0.0003 (12)	−0.0010 (12)	0.0051 (14)
C5	0.0137 (14)	0.0189 (18)	0.0153 (15)	0.0014 (13)	−0.0025 (11)	0.0010 (13)
C6	0.0172 (14)	0.025 (2)	0.0182 (16)	−0.0014 (13)	0.0012 (12)	0.0021 (15)
C7	0.0217 (16)	0.034 (2)	0.0165 (17)	0.0033 (15)	0.0025 (13)	−0.0009 (16)
C8	0.0334 (19)	0.020 (2)	0.0155 (16)	0.0022 (15)	−0.0021 (14)	−0.0022 (14)
C9	0.0275 (17)	0.031 (2)	0.0230 (18)	−0.0104 (15)	−0.0014 (14)	−0.0048 (16)
C10	0.0182 (15)	0.030 (2)	0.0192 (17)	−0.0032 (14)	0.0029 (13)	−0.0042 (16)
C11	0.051 (2)	0.029 (2)	0.0213 (18)	−0.0049 (17)	0.0051 (16)	−0.0064 (16)

Geometric parameters (Å, º) top

Br1—C2	1.995 (3)	C6—C7	1.380 (4)
O1—C4	1.226 (3)	C6—H6	0.9500
N1—C4	1.352 (4)	C7—C8	1.382 (4)
N1—C5	1.416 (4)	C7—H7	0.9500
N1—H1N	0.840 (17)	C8—C9	1.391 (4)
C1—C2	1.519 (4)	C8—C11	1.509 (5)
C1—H1A	0.9800	C9—C10	1.382 (4)
C1—H1B	0.9800	C9—H9	0.9500
C1—H1C	0.9800	C10—H10	0.9500
C2—C3	1.515 (4)	C11—H11A	0.9800
C2—C4	1.533 (4)	C11—H11B	0.9800
C3—H3A	0.9800	C11—H11C	0.9800
C3—H3B	0.9800	C11—H11D	0.9800
C3—H3C	0.9800	C11—H11E	0.9800
C5—C10	1.387 (4)	C11—H11F	0.9800
C5—C6	1.397 (4)

C4—N1—C5	126.2 (2)	C8—C7—H7	118.5
C4—N1—H1N	115 (2)	C7—C8—C9	117.1 (3)
C5—N1—H1N	118 (2)	C7—C8—C11	121.8 (3)
C2—C1—H1A	109.5	C9—C8—C11	121.1 (3)
C2—C1—H1B	109.5	C10—C9—C8	121.2 (3)
H1A—C1—H1B	109.5	C10—C9—H9	119.4
C2—C1—H1C	109.5	C8—C9—H9	119.4
H1A—C1—H1C	109.5	C9—C10—C5	120.8 (3)
H1B—C1—H1C	109.5	C9—C10—H10	119.6
C3—C2—C1	111.2 (3)	C5—C10—H10	119.6
C3—C2—C4	111.1 (2)	C8—C11—H11A	109.5
C1—C2—C4	115.1 (2)	C8—C11—H11B	109.5
C3—C2—Br1	107.0 (2)	H11A—C11—H11B	109.5
C1—C2—Br1	107.20 (19)	C8—C11—H11C	109.5
C4—C2—Br1	104.7 (2)	H11A—C11—H11C	109.5
C2—C3—H3A	109.5	H11B—C11—H11C	109.5
C2—C3—H3B	109.5	C8—C11—H11D	109.5
H3A—C3—H3B	109.5	H11A—C11—H11D	141.1
C2—C3—H3C	109.5	H11B—C11—H11D	56.3
H3A—C3—H3C	109.5	H11C—C11—H11D	56.3
H3B—C3—H3C	109.5	C8—C11—H11E	109.5
O1—C4—N1	123.0 (3)	H11A—C11—H11E	56.3
O1—C4—C2	120.8 (3)	H11B—C11—H11E	141.1
N1—C4—C2	116.2 (2)	H11C—C11—H11E	56.3
C10—C5—C6	118.7 (3)	H11D—C11—H11E	109.5
C10—C5—N1	118.1 (3)	C8—C11—H11F	109.5
C6—C5—N1	123.3 (3)	H11A—C11—H11F	56.3
C7—C6—C5	119.3 (3)	H11B—C11—H11F	56.3
C7—C6—H6	120.4	H11C—C11—H11F	141.1
C5—C6—H6	120.4	H11D—C11—H11F	109.5
C6—C7—C8	122.9 (3)	H11E—C11—H11F	109.5
C6—C7—H7	118.5

C5—N1—C4—O1	4.0 (5)	C10—C5—C6—C7	−1.6 (5)
C5—N1—C4—C2	−177.5 (3)	N1—C5—C6—C7	179.3 (3)
C3—C2—C4—O1	14.6 (4)	C5—C6—C7—C8	−0.4 (5)
C1—C2—C4—O1	142.0 (3)	C6—C7—C8—C9	1.6 (5)
Br1—C2—C4—O1	−100.5 (3)	C6—C7—C8—C11	−178.2 (3)
C3—C2—C4—N1	−163.9 (3)	C7—C8—C9—C10	−1.0 (5)
C1—C2—C4—N1	−36.5 (4)	C11—C8—C9—C10	178.8 (3)
Br1—C2—C4—N1	81.0 (3)	C8—C9—C10—C5	−0.9 (5)
C4—N1—C5—C10	149.7 (3)	C6—C5—C10—C9	2.2 (5)
C4—N1—C5—C6	−31.2 (5)	N1—C5—C10—C9	−178.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (2)	2.13 (2)	2.937 (3)	161 (3)
C1—H1C···O1ⁱ	0.98	2.44	3.382 (4)	162
C10—H10···O1ⁱ	0.95	2.57	3.321 (4)	137

Symmetry code: (i) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄BrNO
M_r	256.14
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	10.0728 (4), 11.2577 (4), 20.3670 (6)
V (Å³)	2309.55 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.53
Crystal size (mm)	0.25 × 0.12 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur E diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.751, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10140, 2762, 1819
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.093, 1.06
No. of reflections	2762
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.46

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.840 (17)	2.13 (2)	2.937 (3)	161 (3)
C1—H1C···O1ⁱ	0.98	2.44	3.382 (4)	162
C10—H10···O1ⁱ	0.95	2.57	3.321 (4)	137

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database (Allen, 2002 ). RMF and FZ also thank the Universidad del Valle, Colombia, and the Instituto de Química de São Carlos, USP, Brazil, for partial financial support.

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