2-Bromo-N-(2-hy­droxy-5-methyl­phen­yl)-2-methyl­propanamide

Moreno-Fuquen, R.; Quintero, D.E.; Zuluaga, F.; Grande, C.; Kennedy, A.R.

doi:10.1107/S1600536811033150

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2446

doi:10.1107/S1600536811033150

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2-Bromo-N-(2-hydroxy-5-methylphenyl)-2-methylpropanamide

Rodolfo Moreno-Fuquen,^a ^* David E. Quintero,^a Fabio Zuluaga,^a Carlos Grande ^b and Alan R. Kennedy ^c

^aDepartamento de Química – Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, ^bDepartamento de Química – Facultad de Ciencias, Universidad ICESI, Santiago de Cali, Colombia, and ^cWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: rodimo26@yahoo.es

(Received 14 August 2011; accepted 16 August 2011; online 27 August 2011)

In the title molecule, C₁₁H₁₄BrNO₂, there is twist between the mean plane of the amide group and the benzene ring [the C—N—C—C torsion angle is −172.1 (2)°]. The amide H atom forms an intramolecular hydrogen bond with the Br atom. In the crystal, intermolecular O—H⋯O and weak C—H⋯O hydrogen bonds link molecules into a chain along [100].

Related literature

For functional initiators in polymerization processes, see: Matyjaszewski & Xia (2001 ); Kato et al. (1995 ). For related structures, see: Moreno-Fuquen et al. (2011a ,b ). For hydrogen-bond graph-set motifs, see: Etter (1990 ).

Experimental

Crystal data

C₁₁H₁₄BrNO₂
M_r = 272.14
Monoclinic, P 2₁ /c
a = 7.4510 (2) Å
b = 13.8498 (4) Å
c = 12.8646 (4) Å
β = 116.324 (2)°
V = 1189.89 (6) Å³
Z = 4
Mo Kα radiation
μ = 3.44 mm⁻¹
T = 123 K
0.30 × 0.10 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.650, T_max = 1.000
5803 measured reflections
2886 independent reflections
2437 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.085
S = 1.05
2886 reflections
147 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 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
O2—H1H⋯O1ⁱ	0.85 (1)	1.81 (1)	2.659 (2)	179 (3)
C1—H1C⋯O2ⁱⁱ	0.98	2.53	3.445 (3)	156
N1—H1N⋯Br1	0.87 (3)	2.47 (3)	3.031 (2)	123 (2)
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 (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/S1600536811033150/tk2780sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033150/tk2780Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033150/tk2780Isup3.cml

checkCIF report

Comment top

The title compound, (I), is part of a search for new functional initiators in polymerization processes (Matyjaszewski & Xia, 2001; Kato et al., 1995), which is carried out by the Polymer Group of Universidad del Valle (Moreno-Fuquen et al., 2011a; Moreno-Fuquen et al., 2011b). The molecular structure of (I) is shown in Fig. 1. There is a twist between the mean plane of the amide group and the benzene ring giving a C4—N1—C5—C6 torsion angle of -172.1 (2) °. This value is very different to that presented in other related systems: [12.7 (4) and -31.2 (5) °, respectively (Moreno-Fuquen et al., 2011a; Moreno-Fuquen et al., 2011b)]. The difference in the value of torsion angle with respect to other related systems, is probably due to the presence of the hydroxyl group in the benzene ring in (I). The crystal packing is stabilized by O—H···O and weak C—H···O intermolecular hydrogen bonds which link the molecules into one dimensional chains along [100] incorporating C(7) graphs motifs (Etter, 1990); see Table 1 and Fig. 2. Additionally, an intramolecular N—H···Br hydrogen bond is observed (Table 1).

Related literature top

For functional initiators in polymerization processes, see: Matyjaszewski & Xia (2001); Kato et al. (1995). For related structures, see: Moreno-Fuquen et al. (2011a,b). For hydrogen-bond graph-set motifs, see: Etter (1990).

Experimental top

2-Hydroxy-5-methyl aniline (3.512 mmol, 0.432 g), triethylamine (0.635 mmol, 0.064 g) were mixed in a 100 mL round bottom flask. Then, a solution of 2-bromo isobutryl bromide (0.807 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 recrystallized from a solution of hexane and ethyl acetate (v/v 80:20). M.pt. 385 (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 (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. Molecular structure of (I) showing atom numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a one dimensional chain along [100]. Dashed lines indicate hydrogen bonds. Symmetry code: (i) 1 + x,+y, z.

2-Bromo-N-(2-hydroxy-5-methylphenyl)-2-methylpropanamide top

Crystal data top

C₁₁H₁₄BrNO₂	F(000) = 552
M_r = 272.14	D_x = 1.519 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 385(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4510 (2) Å	Cell parameters from 3082 reflections
b = 13.8498 (4) Å	θ = 3.1–29.4°
c = 12.8646 (4) Å	µ = 3.44 mm⁻¹
β = 116.324 (2)°	T = 123 K
V = 1189.89 (6) Å³	Tablet, colourless
Z = 4	0.30 × 0.10 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur E diffractometer	2886 independent reflections
Radiation source: fine-focus sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 29.4°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −8→10
T_min = 0.650, T_max = 1.000	k = −16→19
5803 measured reflections	l = −16→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0441P)² + 0.2346P] where P = (F_o² + 2F_c²)/3
2886 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.73 e Å⁻³
1 restraint	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₁H₁₄BrNO₂	V = 1189.89 (6) Å³
M_r = 272.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4510 (2) Å	µ = 3.44 mm⁻¹
b = 13.8498 (4) Å	T = 123 K
c = 12.8646 (4) Å	0.30 × 0.10 × 0.08 mm
β = 116.324 (2)°

Data collection top

Oxford Diffraction Xcalibur E diffractometer	2886 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2437 reflections with I > 2σ(I)
T_min = 0.650, T_max = 1.000	R_int = 0.023
5803 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.73 e Å⁻³
2886 reflections	Δρ_min = −0.46 e Å⁻³
147 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	0.10479 (3)	0.358681 (19)	0.14350 (2)	0.02782 (10)
O1	−0.0362 (3)	0.54556 (15)	0.34215 (18)	0.0387 (5)
O2	0.5930 (2)	0.53566 (12)	0.32150 (14)	0.0219 (4)
N1	0.2461 (3)	0.51979 (14)	0.32142 (17)	0.0190 (4)
C1	−0.1738 (4)	0.35819 (19)	0.2380 (3)	0.0317 (6)
H1A	−0.0742	0.3209	0.3025	0.048*
H1B	−0.2525	0.3146	0.1739	0.048*
H1C	−0.2629	0.3916	0.2638	0.048*
C2	−0.0677 (3)	0.43204 (18)	0.1973 (2)	0.0227 (5)
C3	−0.2146 (4)	0.4905 (2)	0.0933 (2)	0.0375 (7)
H3A	−0.2935	0.4466	0.0296	0.056*
H3B	−0.1398	0.5352	0.0680	0.056*
H3C	−0.3043	0.5272	0.1158	0.056*
C4	0.0531 (3)	0.50331 (18)	0.2951 (2)	0.0215 (5)
C5	0.3773 (3)	0.58845 (16)	0.39924 (19)	0.0162 (4)
C6	0.5634 (3)	0.59619 (17)	0.39643 (19)	0.0177 (4)
C7	0.7014 (3)	0.66329 (17)	0.4661 (2)	0.0220 (5)
H7	0.8263	0.6696	0.4635	0.026*
C8	0.6582 (3)	0.72175 (17)	0.5400 (2)	0.0220 (5)
H8	0.7538	0.7681	0.5870	0.026*
C9	0.4764 (3)	0.71337 (16)	0.54611 (19)	0.0193 (5)
C10	0.3369 (3)	0.64603 (15)	0.4745 (2)	0.0182 (5)
H10	0.2123	0.6396	0.4774	0.022*
C11	0.4344 (4)	0.77409 (18)	0.6301 (2)	0.0261 (5)
H11A	0.4697	0.7376	0.7019	0.039*
H11B	0.2918	0.7907	0.5955	0.039*
H11C	0.5144	0.8334	0.6476	0.039*
H1H	0.711 (2)	0.540 (2)	0.328 (3)	0.038 (8)*
H1N	0.297 (4)	0.4836 (19)	0.286 (2)	0.027 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02120 (15)	0.03380 (17)	0.02828 (15)	0.00141 (11)	0.01082 (11)	−0.01028 (10)
O1	0.0186 (9)	0.0505 (13)	0.0535 (12)	−0.0127 (9)	0.0219 (9)	−0.0306 (10)
O2	0.0130 (8)	0.0300 (9)	0.0261 (9)	−0.0022 (7)	0.0118 (7)	−0.0037 (7)
N1	0.0128 (9)	0.0224 (10)	0.0239 (10)	−0.0013 (8)	0.0100 (8)	−0.0044 (8)
C1	0.0248 (13)	0.0322 (15)	0.0411 (16)	−0.0082 (11)	0.0174 (12)	−0.0120 (12)
C2	0.0149 (11)	0.0267 (13)	0.0256 (12)	0.0011 (10)	0.0082 (9)	−0.0070 (10)
C3	0.0273 (14)	0.0417 (17)	0.0313 (15)	0.0126 (13)	0.0021 (11)	−0.0042 (13)
C4	0.0133 (11)	0.0265 (12)	0.0261 (12)	−0.0020 (10)	0.0101 (9)	−0.0042 (10)
C5	0.0106 (10)	0.0176 (11)	0.0183 (10)	−0.0001 (9)	0.0044 (8)	0.0030 (8)
C6	0.0138 (11)	0.0207 (12)	0.0183 (11)	0.0002 (9)	0.0069 (9)	0.0034 (9)
C7	0.0143 (11)	0.0264 (13)	0.0250 (12)	−0.0049 (10)	0.0084 (9)	0.0024 (10)
C8	0.0174 (11)	0.0216 (12)	0.0230 (12)	−0.0054 (10)	0.0053 (9)	−0.0013 (9)
C9	0.0202 (11)	0.0177 (11)	0.0169 (11)	−0.0003 (10)	0.0056 (9)	0.0025 (9)
C10	0.0139 (11)	0.0206 (12)	0.0207 (11)	0.0004 (9)	0.0081 (9)	0.0024 (9)
C11	0.0277 (13)	0.0257 (13)	0.0241 (12)	−0.0011 (11)	0.0110 (10)	−0.0044 (10)

Geometric parameters (Å, º) top

Br1—C2	1.988 (2)	C3—H3C	0.9800
O1—C4	1.229 (3)	C5—C10	1.387 (3)
O2—C6	1.367 (3)	C5—C6	1.407 (3)
O2—H1H	0.847 (10)	C6—C7	1.381 (3)
N1—C4	1.343 (3)	C7—C8	1.391 (3)
N1—C5	1.412 (3)	C7—H7	0.9500
N1—H1N	0.87 (3)	C8—C9	1.396 (3)
C1—C2	1.520 (3)	C8—H8	0.9500
C1—H1A	0.9800	C9—C10	1.396 (3)
C1—H1B	0.9800	C9—C11	1.508 (3)
C1—H1C	0.9800	C10—H10	0.9500
C2—C3	1.531 (4)	C11—H11A	0.9800
C2—C4	1.537 (3)	C11—H11B	0.9800
C3—H3A	0.9800	C11—H11C	0.9800
C3—H3B	0.9800

C6—O2—H1H	112 (2)	C10—C5—C6	119.7 (2)
C4—N1—C5	128.39 (19)	C10—C5—N1	125.84 (19)
C4—N1—H1N	115.9 (18)	C6—C5—N1	114.43 (19)
C5—N1—H1N	115.7 (18)	O2—C6—C7	124.29 (19)
C2—C1—H1A	109.5	O2—C6—C5	116.13 (19)
C2—C1—H1B	109.5	C7—C6—C5	119.6 (2)
H1A—C1—H1B	109.5	C6—C7—C8	120.2 (2)
C2—C1—H1C	109.5	C6—C7—H7	119.9
H1A—C1—H1C	109.5	C8—C7—H7	119.9
H1B—C1—H1C	109.5	C7—C8—C9	121.0 (2)
C1—C2—C3	112.2 (2)	C7—C8—H8	119.5
C1—C2—C4	110.8 (2)	C9—C8—H8	119.5
C3—C2—C4	107.9 (2)	C8—C9—C10	118.4 (2)
C1—C2—Br1	106.92 (16)	C8—C9—C11	120.6 (2)
C3—C2—Br1	106.75 (16)	C10—C9—C11	121.0 (2)
C4—C2—Br1	112.25 (14)	C5—C10—C9	121.1 (2)
C2—C3—H3A	109.5	C5—C10—H10	119.5
C2—C3—H3B	109.5	C9—C10—H10	119.5
H3A—C3—H3B	109.5	C9—C11—H11A	109.5
C2—C3—H3C	109.5	C9—C11—H11B	109.5
H3A—C3—H3C	109.5	H11A—C11—H11B	109.5
H3B—C3—H3C	109.5	C9—C11—H11C	109.5
O1—C4—N1	123.2 (2)	H11A—C11—H11C	109.5
O1—C4—C2	117.44 (19)	H11B—C11—H11C	109.5
N1—C4—C2	119.26 (19)

C5—N1—C4—O1	−3.6 (4)	C10—C5—C6—C7	−2.1 (3)
C5—N1—C4—C2	173.2 (2)	N1—C5—C6—C7	177.9 (2)
C1—C2—C4—O1	−53.7 (3)	O2—C6—C7—C8	−179.8 (2)
C3—C2—C4—O1	69.5 (3)	C5—C6—C7—C8	1.1 (3)
Br1—C2—C4—O1	−173.2 (2)	C6—C7—C8—C9	0.5 (4)
C1—C2—C4—N1	129.2 (2)	C7—C8—C9—C10	−1.2 (3)
C3—C2—C4—N1	−107.6 (3)	C7—C8—C9—C11	177.4 (2)
Br1—C2—C4—N1	9.8 (3)	C6—C5—C10—C9	1.4 (3)
C4—N1—C5—C10	7.8 (4)	N1—C5—C10—C9	−178.5 (2)
C4—N1—C5—C6	−172.1 (2)	C8—C9—C10—C5	0.2 (3)
C10—C5—C6—O2	178.8 (2)	C11—C9—C10—C5	−178.4 (2)
N1—C5—C6—O2	−1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1H···O1ⁱ	0.85 (1)	1.81 (1)	2.659 (2)	179 (3)
C1—H1C···O2ⁱⁱ	0.98	2.53	3.445 (3)	156
N1—H1N···Br1	0.87 (3)	2.47 (3)	3.031 (2)	123 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄BrNO₂
M_r	272.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	7.4510 (2), 13.8498 (4), 12.8646 (4)
β (°)	116.324 (2)
V (Å³)	1189.89 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.44
Crystal size (mm)	0.30 × 0.10 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur E diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.650, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5803, 2886, 2437
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.085, 1.05
No. of reflections	2886
No. of parameters	147
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.46

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (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
O2—H1H···O1ⁱ	0.847 (10)	1.813 (10)	2.659 (2)	179 (3)
C1—H1C···O2ⁱⁱ	0.98	2.53	3.445 (3)	155.7
N1—H1N···Br1	0.87 (3)	2.47 (3)	3.031 (2)	123 (2)

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

Acknowledgements

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database. RMF and FZ also thank the Universidad del Valle, Colombia, and CG thanks the Universidad ICESI for partial financial support.

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