N,N′-(1,4-Phenyl­ene)bis­(2-bromo-2-methyl­propanamide)

Haridharan, N.; Ramkumar, V.; Dhamodharan, R.

doi:10.1107/S1600536812003479

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o811

doi:10.1107/S1600536812003479

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N,N′-(1,4-Phenylene)bis(2-bromo-2-methylpropanamide)

N. Haridharan,^a V. Ramkumar ^a and R. Dhamodharan ^a ^*

^aDepartment of Chemistry, IIT Madras, Chennai, Tamil nadu, India
^*Correspondence e-mail: damo@iitm.ac.in

(Received 3 November 2011; accepted 26 January 2012; online 24 February 2012)

The molecular structure of the title compound, C₁₄H₁₈Br₂N₂O₂, has one half-molecule in the asymmetric unit. The molecule has a crystallographic inversion centre in the middle of the benzene ring. The C—C—N—C torsion angle between the benzene ring and the bromoamide group is 149.2 (7)°. The crystal is stabilized by a strong intermolecular N—H⋯O bond and weak C—H⋯O interactions. These contacts give rise to a three-dimensional network.

Related literature

For the use of the title compound as an initiator in atom transfer radical polymerization and other polymerization studies, see: Ashraf et al. (1994 ); Domenicano et al. (1977 ); Kuipers et al. (1989 ); Matyjaszewski & Xia (2001 ); Miroshnikova et al. (2007 ); Rollison et al. (2006 ). For similar structures, see: Haridharan et al. (2010 ).

Experimental

Crystal data

C₁₄H₁₈Br₂N₂O₂
M_r = 406.12
Monoclinic, P 2₁ /c
a = 13.834 (3) Å
b = 6.4746 (13) Å
c = 9.4642 (18) Å
β = 103.807 (9)°
V = 823.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 298 K
0.35 × 0.22 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.278, T_max = 0.791
1834 measured reflections
1834 independent reflections
664 reflections with I > 2σ(I)
R_int = 0.000

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.146
S = 0.94
1834 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.23	3.057 (7)	162
C7—H7B⋯O1ⁱ	0.96	2.57	3.503 (9)	164
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003479/bv2195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003479/bv2195Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003479/bv2195Isup3.cml

checkCIF report

Comment top

The title compound C₁₄ H₁₈ Br₂ N₂ O₂ is a difunctional aromatic amide based derivative, which is used as an initiator in Atom Transfer Radical Polymerization (ATRP) (Matyjaszewski et al., (2001). We have already reported a similar ATRP initiator (Haridharan et al., 2010). The title compound reported here is a similar derivative with a diamide functionality (Domenicano et al. (1977); Kuipers et al. (1989). It is mainly used as a component of engineering polymers and composites (Ashraf et al., 1994). It is also an ingredient in hair dyes.

p-Phenylenediamine is a precursor to aramid plastics and fibers such as Kevlar (Rollison et al., 2006). p-Phenylenediamine is also used as a developing agent in the color photographic film development process, reacting with the silver grains in the film and creating the colored dyes that form the image. p-Phenylenediamine derivatives such as chloroquine are the most important and widely used class of drugs for treatment of malaria (Miroshnikova et al., 2007). In the title compound C₁₄H₁₈Br₂N₂O₂, the torsion angle between the phenyl ring and the bromo amide group is 149.2 (7)° (C3—C1—N1—C4). The molecule has a crystallographic inversion centre in the middle of the phenyl ring. The crystal is stabilized by a strong intermolecular N—H···O bonding and weak C-H···O interactions. These contacts gives rise to a three dimensional network.

Related literature top

For the use of the title compound as an initiator in atom transfer radical polymerization and other polymerization studies, see: Ashraf et al. (1994); Domenicano et al. (1977); Kuipers et al. (1989); Matyjaszewski et al. (2001); Miroshnikova et al. (2007); Rollison et al., (2006). For similar structures, see: Haridharan et al. (2010).

Experimental top

p-Phenylene diamine (5 g, 0.012 moles), triethylamine (12 g, 0.05 moles) and THF (400 ml) were placed in a 3-neck round bottomed flask. Bromoisobutyrl bromide (13.7 g, 0.05 moles) was added slowly, using a syringe, with stirring, upon which a brown precipitate of triethylammonium bromide was formed. The mixture was left to react for 12 h, with stirring. Subsequently, triethylammonium bromide, the precipitate was removed by filtration and the THF was removed by rotary evaporation. The resulting crude product was dissolved in ethyl acetate, washed with bicarbonate solution and then with water thrice followed by brine solution and dried over anhydrous sodium sulfate. The resulting solvent was removed by rotary evaporation. The product was purified by column chromatography technique using 10% ethyl acetate in hexane as the eluent to obtain pure initiator as a bright yellow solid. Recrystallization of the compound from hexane gave X-ray diffraction quality crystals of N,N'-(1,4-phenylene)bis(2-bromo-2-methylpropanamide).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP of the molecule with atoms represented as 30% probability ellipsoids.

2-bromo-N-[4-(2-bromo-2-methylpropanamido)phenyl]-2-methylpropanamide top

Crystal data top

C₁₄H₁₈Br₂N₂O₂	F(000) = 404
M_r = 406.12	D_x = 1.638 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1219 reflections
a = 13.834 (3) Å	θ = 0.0–0.0°
b = 6.4746 (13) Å	µ = 4.93 mm⁻¹
c = 9.4642 (18) Å	T = 298 K
β = 103.807 (9)°	Block, colourless
V = 823.2 (3) Å³	0.35 × 0.22 × 0.05 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1834 independent reflections
Radiation source: fine-focus sealed tube	664 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
ϕ and ω scans	θ_max = 27.8°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −18→17
T_min = 0.278, T_max = 0.791	k = 0→8
1834 measured reflections	l = 0→11

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0575P)²] where P = (F_o² + 2F_c²)/3
1834 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₁₄H₁₈Br₂N₂O₂	V = 823.2 (3) Å³
M_r = 406.12	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.834 (3) Å	µ = 4.93 mm⁻¹
b = 6.4746 (13) Å	T = 298 K
c = 9.4642 (18) Å	0.35 × 0.22 × 0.05 mm
β = 103.807 (9)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1834 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	664 reflections with I > 2σ(I)
T_min = 0.278, T_max = 0.791	R_int = 0.000
1834 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 0.94	Δρ_max = 0.54 e Å⁻³
1834 reflections	Δρ_min = −0.56 e Å⁻³
93 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	0.90343 (6)	0.80012 (14)	0.54184 (10)	0.0699 (4)
O1	0.7011 (3)	0.5876 (8)	0.6804 (5)	0.0520 (14)
N1	0.6647 (4)	0.7640 (8)	0.4699 (6)	0.0436 (16)
H1A	0.6809	0.7779	0.3882	0.052*
C1	0.5804 (5)	0.8774 (11)	0.4872 (7)	0.0364 (18)
C2	0.5188 (5)	0.8134 (11)	0.5735 (8)	0.050 (2)
H2	0.5308	0.6887	0.6234	0.060*
C3	0.5607 (5)	1.0646 (13)	0.4144 (7)	0.045 (2)
H3	0.6021	1.1089	0.3561	0.054*
C4	0.7212 (5)	0.6389 (10)	0.5664 (8)	0.0366 (18)
C5	0.8137 (4)	0.5549 (10)	0.5272 (7)	0.0387 (18)
C6	0.8682 (6)	0.4020 (14)	0.6398 (9)	0.079 (3)
H6A	0.8881	0.4692	0.7327	0.118*
H6B	0.9261	0.3518	0.6116	0.118*
H6C	0.8250	0.2884	0.6465	0.118*
C7	0.7975 (5)	0.4668 (11)	0.3732 (7)	0.051 (2)
H7A	0.8601	0.4226	0.3567	0.076*
H7B	0.7693	0.5714	0.3036	0.076*
H7C	0.7529	0.3512	0.3627	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0573 (6)	0.0714 (7)	0.0882 (8)	−0.0096 (5)	0.0316 (4)	−0.0175 (5)
O1	0.056 (3)	0.074 (4)	0.035 (3)	0.008 (3)	0.028 (3)	0.009 (3)
N1	0.053 (4)	0.056 (4)	0.032 (4)	0.018 (3)	0.028 (3)	0.011 (3)
C1	0.040 (4)	0.046 (5)	0.028 (4)	0.003 (3)	0.018 (3)	0.000 (4)
C2	0.056 (5)	0.050 (5)	0.052 (5)	0.013 (4)	0.027 (4)	0.018 (4)
C3	0.043 (4)	0.066 (6)	0.033 (5)	0.010 (4)	0.026 (3)	0.009 (4)
C4	0.045 (4)	0.032 (5)	0.038 (5)	0.007 (3)	0.021 (4)	0.004 (4)
C5	0.037 (4)	0.044 (5)	0.041 (5)	0.012 (4)	0.022 (3)	0.012 (4)
C6	0.095 (7)	0.092 (7)	0.062 (6)	0.042 (6)	0.044 (5)	0.028 (5)
C7	0.076 (5)	0.041 (5)	0.046 (5)	0.013 (4)	0.036 (4)	−0.006 (4)

Geometric parameters (Å, º) top

Br1—C5	2.000 (7)	C3—H3	0.9300
O1—C4	1.223 (7)	C4—C5	1.516 (8)
N1—C4	1.326 (8)	C5—C6	1.517 (9)
N1—C1	1.421 (8)	C5—C7	1.531 (9)
N1—H1A	0.8600	C6—H6A	0.9600
C1—C2	1.377 (8)	C6—H6B	0.9600
C1—C3	1.389 (9)	C6—H6C	0.9600
C2—C3ⁱ	1.381 (9)	C7—H7A	0.9600
C2—H2	0.9300	C7—H7B	0.9600
C3—C2ⁱ	1.381 (9)	C7—H7C	0.9600

C4—N1—C1	127.0 (5)	C6—C5—C7	111.2 (6)
C4—N1—H1A	116.5	C4—C5—Br1	104.2 (4)
C1—N1—H1A	116.5	C6—C5—Br1	105.8 (5)
C2—C1—C3	118.8 (6)	C7—C5—Br1	108.0 (4)
C2—C1—N1	123.6 (7)	C5—C6—H6A	109.5
C3—C1—N1	117.6 (5)	C5—C6—H6B	109.5
C1—C2—C3ⁱ	119.7 (7)	H6A—C6—H6B	109.5
C1—C2—H2	120.2	C5—C6—H6C	109.5
C3ⁱ—C2—H2	120.2	H6A—C6—H6C	109.5
C2ⁱ—C3—C1	121.6 (6)	H6B—C6—H6C	109.5
C2ⁱ—C3—H3	119.2	C5—C7—H7A	109.5
C1—C3—H3	119.2	C5—C7—H7B	109.5
O1—C4—N1	123.5 (6)	H7A—C7—H7B	109.5
O1—C4—C5	120.1 (6)	C5—C7—H7C	109.5
N1—C4—C5	116.4 (6)	H7A—C7—H7C	109.5
C4—C5—C6	111.7 (5)	H7B—C7—H7C	109.5
C4—C5—C7	115.2 (6)

C4—N1—C1—C2	−29.5 (11)	C1—N1—C4—C5	−173.4 (6)
C4—N1—C1—C3	149.4 (7)	O1—C4—C5—C6	2.8 (10)
C3—C1—C2—C3ⁱ	0.1 (12)	N1—C4—C5—C6	−175.8 (7)
N1—C1—C2—C3ⁱ	179.0 (6)	O1—C4—C5—C7	130.9 (7)
C2—C1—C3—C2ⁱ	−0.2 (12)	N1—C4—C5—C7	−47.8 (8)
N1—C1—C3—C2ⁱ	−179.1 (6)	O1—C4—C5—Br1	−111.0 (6)
C1—N1—C4—O1	8.0 (11)	N1—C4—C5—Br1	70.4 (7)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.86	2.23	3.057 (7)	162
C7—H7B···O1ⁱⁱ	0.96	2.57	3.503 (9)	164

Symmetry code: (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈Br₂N₂O₂
M_r	406.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.834 (3), 6.4746 (13), 9.4642 (18)
β (°)	103.807 (9)
V (Å³)	823.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.93
Crystal size (mm)	0.35 × 0.22 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.278, 0.791
No. of measured, independent and observed [I > 2σ(I)] reflections	1834, 1834, 664
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.146, 0.94
No. of reflections	1834
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.56

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.23	3.057 (7)	161.7
C7—H7B···O1ⁱ	0.96	2.57	3.503 (9)	164.3

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

The authors acknowledge the Department of Chemistry, IIT Madras, for the single-crystal X-ray data collection.

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