N,N-Bis(2-bromo­ethyl)aniline

Bojan, R.V.; Varga, R.A.; Silvestru, C.

doi:10.1107/S1600536807056279

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o86

https://doi.org/10.1107/S1600536807056279

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N,N-Bis(2-bromoethyl)aniline

R. Vilma Bojan,^a ^* Richard A. Varga ^a and Cristian Silvestru ^a

^aFacultatea de Chimie si Inginerie Chimica, Univesitatea Babes-Bolyai, Cluj-Napoca, Ro-40028, Romania
^*Correspondence e-mail: brvilma@chem.ubbcluj.ro

(Received 3 November 2007; accepted 6 November 2007; online 6 December 2007)

The molecule of the title compound, C₁₀H₁₃Br₂N, has a twofold rotation axis along the N—C_phenyl bond. The compound shows a slightly distorted trigonal planar geometry around the N atom. The structural study shows the presence of intermolecular C—H⋯Br interactions, resulting in a three-dimensional supramolecular architecture.

Related literature

For related literature, see: Bricks et al. (2005 ); Chapman & Triggle (1963 ); Ross (1949 ); Hartley et al. (2000 ); Palmer et al. (1990 ); Panthananickal et al. (1978 ).

Experimental

Crystal data

C₁₀H₁₃Br₂N
M_r = 307.03
Orthorhombic, F d d 2
a = 13.682 (12) Å
b = 13.926 (12) Å
c = 12.215 (10) Å
V = 2327 (3) Å³
Z = 8
Mo Kα radiation
μ = 6.92 mm⁻¹
T = 297 (2) K
0.27 × 0.23 × 0.09 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.155, T_max = 0.534
4145 measured reflections
1191 independent reflections
893 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.088
S = 0.99
1191 reflections
61 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.41 e Å⁻³
Absolute structure: Flack (1983 ), 564 Friedel pairs
Flack parameter: 0.05 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯Br1ⁱ	0.97	3.05	3.933 (6)	153
Symmetry code: (i) $[-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2007 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807056279/cf2168sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807056279/cf2168Isup2.hkl

checkCIF report

Comment top

N,N-Bis(2-halogenoalkyl)anilines are widely prepared compounds due to their potential pharmacological activity (Ross, 1949; Chapman & Triggle, 1963; Panthananickal et al., 1978; Palmer et al., 1990). The most common preparation method uses the corresponding alcohol, which upon reaction with a halogenating agent gives the desired aniline derivative (Ross, 1949; Chapman & Triggle, 1963). Some derivatives show anti-adrenaline and anti-noradrenalin activities and have also been investigated as anticancer drugs (Palmer et al., 1990). The great variety of obtainable derivatives upon changing the alkyl or the aryl group bonded to the nitrogen atom has made this type of compounds applicable as starting materials in the synthesis of macrocycles (Bricks et al., 2005; Hartley et al., 2000). The title compound was prepared according to a general method described in the literature starting from N,N-bis(2-hydroxyethyl)aniline, which was treated with PBr₃ (Ross, 1949).

The isolated N,N-bis(2-bromoethyl)aniline crystallizes from benzene. The molecule has a twofold rotation axis through the N—C_phenyl bond (Fig. 1). The bond angles around the N1 atom [C1—N1—C5 = 120.7 (3)° and C5—N1—C5ⁱ 118.6 (6)°; symmetry code: (i) 0.5 - x, 0.5 - y, z] are consistent with a trigonal planar geometry and thus an sp² nature can be considered due to conjugation with the phenyl ring. The sructural analysis shows the presence of intermolecular C—H···Br interactions in the crystal structure. One molecule of N,N-bis(2-bromoethyl)aniline forms interactions with four neighboring molecules [H5···Br1ⁱⁱ = 3.05 Å; symmetry code: (ii) -x + 3/4, y + 1/4, z - 1/4] (Fig. 2). These interactions result in a three-dimensional supramolecular architecture (Fig. 3).

Related literature top

For related literature, see: Bricks et al. (2005); Chapman & Triggle (1963); Ross (1949); Hartley et al. (2000); Palmer et al. (1990); Panthananickal et al. (1978).

Experimental top

Colourless crystals of N,N-bis(2-bromoethyl)aniline, prepared according to the literature (Ross, 1949), were obtained from benzene. The compound was also characterized by ¹H, ¹³C and two-dimensional NMR spectroscopy in CDCl₃ solution. NMR data: ¹H NMR (300 MHz): δ 3.47 (t, 4H, CH₂Br, ³J_HH = 7.4 Hz), 3.79 (t, 4H, CH₂N, ³J_HH = 7.4 Hz), 6.75 (d, 2H, H_o, ³J_HH = 8.3 Hz), 6.84 (t, 1H, H_p, ³J_HH = 7.3 Hz), 7.30 (m, 2H, H_m, ³J_HH = 7.5 Hz); ¹³C NMR (75.5 MHz): δ 27.95 (s, CH₂Br), 53.47 (s, CH₂N), 112.35 (s, C_o), 118.43 (s, C_p), 129.80 (s, C_m), 145.14 (s, C_i).

Structure description top

For related literature, see: Bricks et al. (2005); Chapman & Triggle (1963); Ross (1949); Hartley et al. (2000); Palmer et al. (1990); Panthananickal et al. (1978).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus(Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL(Bruker, 2001); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top

	Fig. 1. : The molecular structure, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have arbitrary radii. Symmetry code: (i) 0.5 - x, 0.5 - y, z.
	Fig. 2. : Hydrogen-bonded framework (dashed lines) in the title compound. Symmetry codes: (i) 0.5 - x, 0.5 - y, z; (ii) -x + 3/4, y + 1/4, z - 1/4.
	Fig. 3. : The crystal packing of the title compound, with hydrogen bonds shown as dashed lines.

N,N-Bis(2-bromoethyl)aniline top

Crystal data top

C₁₀H₁₃Br₂N	F(000) = 1200
M_r = 307.03	D_x = 1.752 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1908 reflections
a = 13.682 (12) Å	θ = 2.7–24.3°
b = 13.926 (12) Å	µ = 6.92 mm⁻¹
c = 12.215 (10) Å	T = 297 K
V = 2327 (3) Å³	Block, colourless
Z = 8	0.27 × 0.23 × 0.09 mm

Data collection top

Bruker SMART APEX diffractometer	1191 independent reflections
Radiation source: fine-focus sealed tube	893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
φ and ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→17
T_min = 0.155, T_max = 0.534	k = −17→17
4145 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0396P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
1191 reflections	Δρ_max = 0.61 e Å⁻³
61 parameters	Δρ_min = −0.41 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 564 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (3)

Crystal data top

C₁₀H₁₃Br₂N	V = 2327 (3) Å³
M_r = 307.03	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 13.682 (12) Å	µ = 6.92 mm⁻¹
b = 13.926 (12) Å	T = 297 K
c = 12.215 (10) Å	0.27 × 0.23 × 0.09 mm

Data collection top

Bruker SMART APEX diffractometer	1191 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	893 reflections with I > 2σ(I)
T_min = 0.155, T_max = 0.534	R_int = 0.047
4145 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.088	Δρ_max = 0.61 e Å⁻³
S = 0.99	Δρ_min = −0.41 e Å⁻³
1191 reflections	Absolute structure: Flack (1983), 564 Friedel pairs
61 parameters	Absolute structure parameter: 0.05 (3)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C6	0.4227 (4)	0.2321 (4)	0.3885 (5)	0.0665 (14)
H6A	0.4458	0.2250	0.4632	0.080*
H6B	0.4729	0.2653	0.3472	0.080*
C5	0.3302 (4)	0.2919 (4)	0.3884 (4)	0.0595 (14)
H5A	0.3448	0.3544	0.4193	0.071*
H5B	0.3097	0.3016	0.3132	0.071*
Br1	0.40184 (5)	0.10577 (5)	0.32538 (10)	0.0854 (3)
C1	0.2500	0.2500	0.5638 (6)	0.0453 (14)
N1	0.2500	0.2500	0.4487 (4)	0.0521 (13)
C2	0.3190 (3)	0.3010 (4)	0.6240 (4)	0.0569 (13)
H2	0.3669	0.3356	0.5871	0.068*
C3	0.3183 (5)	0.3014 (4)	0.7376 (5)	0.0687 (16)
H3	0.3649	0.3371	0.7753	0.082*
C4	0.2500	0.2500	0.7949 (7)	0.074 (2)
H4	0.2500	0.2500	0.8710	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.053 (3)	0.067 (3)	0.079 (4)	−0.001 (2)	0.012 (3)	−0.004 (3)
C5	0.071 (3)	0.052 (3)	0.056 (3)	0.007 (3)	0.008 (3)	0.008 (2)
Br1	0.0888 (4)	0.0783 (4)	0.0891 (4)	0.0256 (3)	0.0001 (4)	−0.0161 (4)
C1	0.047 (3)	0.036 (3)	0.053 (4)	0.012 (3)	0.000	0.000
N1	0.044 (3)	0.062 (3)	0.051 (3)	0.000 (3)	0.000	0.000
C2	0.045 (3)	0.051 (3)	0.075 (3)	−0.004 (2)	−0.004 (2)	−0.007 (3)
C3	0.061 (3)	0.069 (4)	0.076 (4)	0.015 (3)	−0.025 (3)	−0.014 (3)
C4	0.078 (6)	0.083 (6)	0.062 (5)	0.019 (5)	0.000	0.000

Geometric parameters (Å, º) top

C6—C5	1.515 (7)	C1—C2	1.391 (6)
C6—Br1	1.942 (6)	C1—N1	1.406 (9)
C6—H6A	0.970	C2—C3	1.388 (8)
C6—H6B	0.970	C2—H2	0.930
C5—N1	1.445 (6)	C3—C4	1.370 (8)
C5—H5A	0.970	C3—H3	0.930
C5—H5B	0.970	C4—H4	0.930

C5—C6—Br1	112.0 (4)	C2—C1—N1	121.9 (3)
C5—C6—H6A	109.2	C1—N1—C5	120.7 (3)
Br1—C6—H6A	109.2	C1—N1—C5ⁱ	120.7 (3)
C5—C6—H6B	109.2	C5—N1—C5ⁱ	118.6 (6)
Br1—C6—H6B	109.2	C3—C2—C1	121.7 (5)
H6A—C6—H6B	107.9	C3—C2—H2	119.1
N1—C5—C6	114.3 (4)	C1—C2—H2	119.1
N1—C5—H5A	108.7	C4—C3—C2	120.9 (6)
C6—C5—H5A	108.7	C4—C3—H3	119.6
N1—C5—H5B	108.7	C2—C3—H3	119.6
C6—C5—H5B	108.7	C3—C4—C3ⁱ	118.6 (8)
H5A—C5—H5B	107.6	C3—C4—H4	120.7
C2ⁱ—C1—C2	116.2 (7)	C3ⁱ—C4—H4	120.7
C2ⁱ—C1—N1	121.9 (3)

Br1—C6—C5—N1	59.5 (6)	C6—C5—N1—C5ⁱ	−105.7 (5)
C2ⁱ—C1—N1—C5	−171.0 (3)	C2ⁱ—C1—C2—C3	−0.5 (4)
C2—C1—N1—C5	9.0 (3)	N1—C1—C2—C3	179.5 (4)
C2ⁱ—C1—N1—C5ⁱ	8.9 (3)	C1—C2—C3—C4	1.1 (7)
C2—C1—N1—C5ⁱ	−171.1 (3)	C2—C3—C4—C3ⁱ	−0.5 (4)
C6—C5—N1—C1	74.3 (5)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···Br1ⁱⁱ	0.97	3.05	3.933 (6)	153

Symmetry code: (ii) −x+3/4, y+1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃Br₂N
M_r	307.03
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	297
a, b, c (Å)	13.682 (12), 13.926 (12), 12.215 (10)
V (Å³)	2327 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.92
Crystal size (mm)	0.27 × 0.23 × 0.09

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.155, 0.534
No. of measured, independent and observed [I > 2σ(I)] reflections	4145, 1191, 893
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.088, 0.99
No. of reflections	1191
No. of parameters	61
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.41
Absolute structure	Flack (1983), 564 Friedel pairs
Absolute structure parameter	0.05 (3)

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SAINT-Plus(Bruker, 2000), SHELXTL (Bruker, 2001), SHELXTL(Bruker, 2001), DIAMOND (Brandenburg & Putz, 2006), publCIF (Westrip, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···Br1ⁱ	0.97	3.05	3.933 (6)	153

Symmetry code: (i) −x+3/4, y+1/4, z−1/4.

Acknowledgements

Financial support from CNCSIS 2/397/2007 is gratefully acknowledged. The authors also thank the National Center for X-Ray Diffraction, Cluj-Napoca, for help with the structure determination.

References

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