4-[(4-Bromo­phen­yl)diazen­yl]-2-eth­oxy­aniline

Melardi, M.R.; Attar Gharamaleki, J.; Rezabeyk, S.; Rofouei, M.K.

doi:10.1107/S160053681104877X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3396

https://doi.org/10.1107/S160053681104877X

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4-[(4-Bromophenyl)diazenyl]-2-ethoxyaniline

Mohammad Reza Melardi,^a ^* Jafar Attar Gharamaleki,^b Soheyla Rezabeyk ^a and Mohammad Kazem Rofouei ^b

^aDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, and ^bFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
^*Correspondence e-mail: m.melardi@kiau.ac.ir

(Received 28 October 2011; accepted 16 November 2011; online 23 November 2011)

The title compound, C₁₄H₁₄BrN₃O, exhibits a trans geometry about the –N=N– double bond. The dihedral angle between the benzene rings is 24.01 (5)°. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, intermolecular N—H⋯N hydrogen bonds between the amine groups lead to the formation of a C(8) polymeric chain along [101].

Related literature

For the synthesis and crystal structures of similar diazenyl compounds, see: de Wit et al. (2008 ); Yazici et al. (2006 ). For crystal structure of a chloro analogue of the title compound, see: Rofouei et al. (2011 ). For graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₄BrN₃O
M_r = 320.19
Monoclinic, P 2₁ /n
a = 13.219 (2) Å
b = 8.8289 (17) Å
c = 13.506 (2) Å
β = 118.855 (6)°
V = 1380.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.97 mm⁻¹
T = 200 K
0.40 × 0.20 × 0.10 mm

Data collection

Bruker SMART X2S benchtop diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.383, T_max = 0.755
8299 measured reflections
2408 independent reflections
1775 reflections with I > 2Σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.198
S = 1.00
2408 reflections
178 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.98 e Å⁻³
Δρ_min = −1.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.88 (1)	2.38 (2)	3.228 (6)	163 (5)
N3—H3B⋯O1	0.88 (1)	2.28 (5)	2.628 (5)	103 (4)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART X2S (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681104877X/pv2476sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681104877X/pv2476Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681104877X/pv2476Isup3.cml

checkCIF report

Comment top

We have recenly reported the crystal structure of 4-[(4-chlorophenyl)diazenyl]-3-methoxyaniline (Rofouei et al., 2011), a chloro analogue of the title compound. Diazenyl compounds characterized by having a diazo group (—N═N—) commonly adopt the trans configuration in the ground state. In continuation to our work in this field, we now report the crystal structure of the title compound.

The title molecule (Fig. 1) adopts a trans configuration about the –N1═N2– double bond and the C1—N1—N2—C9 dihedral angle is 177.3 (4)°. The molecular dimensions in the title compound are similar to the corresponding dimensions reported in other azo compounds (Yazici et al., 2006; de Wit et al., 2008; Rofouei et al., 2011).

In the structure of the title compound, the molecules are linked into chain-like polymers along the c axis, with C(8) graph set motif (Bernstein et al., 1995), through N3—H3A···N2ⁱ hydrogen bonds with D···A separation of 3.228 (6) Å (Fig. 2 and Tab. 1). The structure is further consolidated by N3—H3A···O1 intramolecular hydrogen bond with D···A separation of 2.628 (5) Å.

Related literature top

For the synthesis and crystal structures of similar diazenyl compounds, see: de Wit et al. (2008); Yazici et al. (2006). For crystal structure of a chloro analogue of the title compound, see: Rofouei et al. (2011). For graph-set motifs, see: Bernstein et al. (1995).

Experimental top

To a 100 ml flask in an ice bath, was added (0.349 g, 2 mmol) p-boromoaniline and (3.65 g, 0.1 mol) of HCl (d = 1.18 g.ml^-1). To the obtained solution, was added dropwise a solution of sodium nitrite (0.14 g in 5 ml H₂O). Then, a diluted solution of o-ethoxyaniline (0.244 g, 2 mmol) in methanol (5 ml) was added to the above solution. The pH of the solution was adjusted at about 6–7 by adding a solution of 10% of sodium acetate. The solution was stirred for about an hour, giving an orange precipitate. It was then filtered off and dried in vacuum. After dissolving in diethylether and recrystallization, red crystals of the title compound were obtained. M.p. 373–376 K.

Structure description top

For the synthesis and crystal structures of similar diazenyl compounds, see: de Wit et al. (2008); Yazici et al. (2006). For crystal structure of a chloro analogue of the title compound, see: Rofouei et al. (2011). For graph-set motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: SMART X2S (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, displacement ellipsoids are drawn at 50% probability level.
	Fig. 2. A part of the unit cell showing N3—H3A···N2 hydrogen bonds, to produce polymeric chain of the title molecules along the c axis.

4-[(4-Bromophenyl)diazenyl]-2-ethoxyaniline top

Crystal data top

C₁₄H₁₄BrN₃O	F(000) = 648
M_r = 320.19	D_x = 1.540 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2935 reflections
a = 13.219 (2) Å	θ = 2.9–24.8°
b = 8.8289 (17) Å	µ = 2.97 mm⁻¹
c = 13.506 (2) Å	T = 200 K
β = 118.855 (6)°	Block, yellow
V = 1380.6 (4) Å³	0.40 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART X2S benchtop diffractometer	2408 independent reflections
Radiation source: fine-focus sealed tube	1775 reflections with I > 2Σ(I)
Graphite monochromator	R_int = 0.075
Detector resolution: 8.33 pixels mm^-1	θ_max = 25.0°, θ_min = 1.8°
ω scans	h = −15→13
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −10→10
T_min = 0.383, T_max = 0.755	l = −16→16
8299 measured reflections

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.198	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.1373P)²] where P = (F_o² + 2F_c²)/3
2408 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.98 e Å⁻³
2 restraints	Δρ_min = −1.11 e Å⁻³

Crystal data top

C₁₄H₁₄BrN₃O	V = 1380.6 (4) Å³
M_r = 320.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.219 (2) Å	µ = 2.97 mm⁻¹
b = 8.8289 (17) Å	T = 200 K
c = 13.506 (2) Å	0.40 × 0.20 × 0.10 mm
β = 118.855 (6)°

Data collection top

Bruker SMART X2S benchtop diffractometer	2408 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1775 reflections with I > 2Σ(I)
T_min = 0.383, T_max = 0.755	R_int = 0.075
8299 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	2 restraints
wR(F²) = 0.198	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.98 e Å⁻³
2408 reflections	Δρ_min = −1.11 e Å⁻³
178 parameters

Special details top

Experimental. ¹H NMR (300 MHz, d⁶-DMSO): 1.31 (3H, CH₃), 4.10 (2H, OCH₂), 6.72–7.68 (7H, aromatic ring) and 5.87 (2H, NH₂ groups). ¹³C NMR (100 MHz, DMSO): 14.63 (CH₃), 63.44 (OCH₂), 101.60–151.34 (C atoms of aromatic rings).

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
Br1	0.62107 (6)	0.84573 (8)	0.08362 (5)	0.0740 (4)
O1	−0.1368 (3)	0.1305 (4)	−0.0555 (3)	0.0469 (9)
N1	0.1207 (4)	0.4681 (5)	−0.1255 (3)	0.0441 (10)
N2	0.1867 (4)	0.4891 (4)	−0.0227 (3)	0.0444 (10)
N3	−0.2711 (4)	0.1068 (5)	−0.2750 (4)	0.0477 (11)
H3A	−0.296 (5)	0.071 (6)	−0.343 (2)	0.057*
H3B	−0.270 (5)	0.039 (5)	−0.227 (3)	0.057*
C1	0.0220 (4)	0.3782 (5)	−0.1537 (4)	0.0380 (11)
C2	−0.0054 (4)	0.3036 (5)	−0.0774 (4)	0.0396 (11)
H2	0.0424	0.3161	0.0018	0.047*
C3	−0.1012 (4)	0.2134 (5)	−0.1179 (4)	0.0364 (11)
C4	−0.1750 (4)	0.1953 (5)	−0.2364 (4)	0.0368 (11)
C5	−0.1446 (4)	0.2697 (5)	−0.3088 (4)	0.0399 (11)
H5	−0.1917	0.2580	−0.3881	0.048*
C6	−0.0488 (5)	0.3591 (5)	−0.2688 (4)	0.0438 (13)
H6	−0.0305	0.4089	−0.3205	0.053*
C7	−0.0682 (5)	0.1345 (6)	0.0658 (4)	0.0454 (13)
H7A	−0.0598	0.2399	0.0937	0.054*
H7B	0.0096	0.0923	0.0900	0.054*
C8	−0.1313 (5)	0.0403 (7)	0.1108 (4)	0.0601 (15)
H8A	−0.0876	0.0388	0.1936	0.090*
H8B	−0.1396	−0.0633	0.0818	0.090*
H8C	−0.2079	0.0839	0.0864	0.090*
C9	0.2870 (4)	0.5761 (5)	−0.0032 (4)	0.0429 (12)
C10	0.3484 (5)	0.6451 (5)	0.0999 (4)	0.0472 (13)
H10	0.3240	0.6346	0.1552	0.057*
C11	0.4442 (4)	0.7285 (6)	0.1237 (4)	0.0461 (12)
H11	0.4841	0.7798	0.1940	0.055*
C12	0.4832 (4)	0.7385 (6)	0.0462 (4)	0.0479 (13)
C13	0.4241 (6)	0.6680 (7)	−0.0578 (5)	0.0611 (17)
H13	0.4510	0.6746	−0.1115	0.073*
C14	0.3252 (5)	0.5878 (7)	−0.0819 (4)	0.0566 (15)
H14	0.2829	0.5401	−0.1534	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0634 (5)	0.0968 (6)	0.0643 (5)	−0.0445 (4)	0.0328 (4)	−0.0213 (3)
O1	0.043 (2)	0.060 (2)	0.0371 (17)	−0.0123 (17)	0.0188 (17)	−0.0022 (15)
N1	0.046 (3)	0.043 (2)	0.040 (2)	−0.0016 (19)	0.018 (2)	0.0031 (17)
N2	0.049 (3)	0.043 (2)	0.043 (2)	0.0051 (19)	0.024 (2)	0.0064 (18)
N3	0.045 (3)	0.055 (3)	0.041 (2)	−0.014 (2)	0.019 (2)	−0.0120 (19)
C1	0.034 (3)	0.037 (2)	0.044 (3)	−0.002 (2)	0.020 (2)	−0.0029 (19)
C2	0.031 (3)	0.043 (2)	0.039 (2)	0.000 (2)	0.012 (2)	−0.001 (2)
C3	0.031 (3)	0.038 (2)	0.042 (3)	0.001 (2)	0.019 (2)	−0.002 (2)
C4	0.032 (3)	0.035 (2)	0.043 (3)	0.001 (2)	0.018 (2)	−0.0042 (19)
C5	0.041 (3)	0.043 (3)	0.037 (3)	−0.001 (2)	0.020 (2)	−0.005 (2)
C6	0.055 (3)	0.036 (2)	0.049 (3)	0.000 (2)	0.031 (3)	−0.002 (2)
C7	0.049 (3)	0.049 (3)	0.037 (3)	−0.001 (2)	0.019 (2)	−0.001 (2)
C8	0.068 (4)	0.060 (3)	0.050 (3)	−0.010 (3)	0.028 (3)	0.005 (3)
C9	0.044 (3)	0.043 (3)	0.045 (3)	0.000 (2)	0.023 (2)	0.005 (2)
C10	0.050 (3)	0.049 (3)	0.046 (3)	−0.004 (2)	0.025 (3)	0.002 (2)
C11	0.049 (3)	0.047 (3)	0.036 (3)	−0.004 (2)	0.017 (2)	0.000 (2)
C12	0.040 (3)	0.054 (3)	0.046 (3)	−0.012 (2)	0.018 (2)	0.001 (2)
C13	0.062 (4)	0.081 (4)	0.050 (3)	−0.034 (3)	0.035 (3)	−0.016 (3)
C14	0.050 (3)	0.068 (4)	0.043 (3)	−0.014 (3)	0.015 (3)	−0.010 (3)

Geometric parameters (Å, º) top

Br1—C12	1.893 (5)	C6—H6	0.9500
O1—C3	1.361 (6)	C7—C8	1.498 (8)
O1—C7	1.439 (6)	C7—H7A	0.9900
N1—N2	1.246 (5)	C7—H7B	0.9900
N1—C1	1.412 (6)	C8—H8A	0.9800
N2—C9	1.442 (7)	C8—H8B	0.9800
N3—C4	1.363 (7)	C8—H8C	0.9800
N3—H3A	0.876 (10)	C9—C10	1.371 (7)
N3—H3B	0.879 (10)	C9—C14	1.383 (8)
C1—C6	1.384 (7)	C10—C11	1.363 (7)
C1—C2	1.410 (7)	C10—H10	0.9500
C2—C3	1.367 (7)	C11—C12	1.375 (7)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.424 (7)	C12—C13	1.383 (7)
C4—C5	1.388 (7)	C13—C14	1.380 (9)
C5—C6	1.363 (7)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500

C3—O1—C7	118.4 (4)	O1—C7—H7B	110.5
N2—N1—C1	116.3 (4)	C8—C7—H7B	110.5
N1—N2—C9	111.8 (4)	H7A—C7—H7B	108.7
C4—N3—H3A	114 (4)	C7—C8—H8A	109.5
C4—N3—H3B	116 (4)	C7—C8—H8B	109.5
H3A—N3—H3B	113 (5)	H8A—C8—H8B	109.5
C6—C1—C2	119.4 (4)	C7—C8—H8C	109.5
C6—C1—N1	114.1 (4)	H8A—C8—H8C	109.5
C2—C1—N1	126.5 (4)	H8B—C8—H8C	109.5
C3—C2—C1	119.6 (4)	C10—C9—C14	119.4 (5)
C3—C2—H2	120.2	C10—C9—N2	117.6 (5)
C1—C2—H2	120.2	C14—C9—N2	123.0 (5)
O1—C3—C2	126.5 (4)	C11—C10—C9	120.4 (5)
O1—C3—C4	112.5 (4)	C11—C10—H10	119.8
C2—C3—C4	121.0 (4)	C9—C10—H10	119.8
N3—C4—C5	122.3 (4)	C10—C11—C12	120.2 (5)
N3—C4—C3	120.0 (4)	C10—C11—H11	119.9
C5—C4—C3	117.7 (4)	C12—C11—H11	119.9
C6—C5—C4	121.6 (4)	C11—C12—C13	120.6 (5)
C6—C5—H5	119.2	C11—C12—Br1	119.7 (4)
C4—C5—H5	119.2	C13—C12—Br1	119.7 (4)
C5—C6—C1	120.8 (5)	C14—C13—C12	118.4 (5)
C5—C6—H6	119.6	C14—C13—H13	120.8
C1—C6—H6	119.6	C12—C13—H13	120.8
O1—C7—C8	106.3 (4)	C13—C14—C9	120.9 (5)
O1—C7—H7A	110.5	C13—C14—H14	119.6
C8—C7—H7A	110.5	C9—C14—H14	119.6

C1—N1—N2—C9	177.3 (4)	C2—C1—C6—C5	0.2 (7)
N2—N1—C1—C6	179.6 (4)	N1—C1—C6—C5	177.1 (4)
N2—N1—C1—C2	−3.8 (7)	C3—O1—C7—C8	177.1 (5)
C6—C1—C2—C3	0.2 (7)	N1—N2—C9—C10	161.2 (5)
N1—C1—C2—C3	−176.3 (5)	N1—N2—C9—C14	−21.2 (7)
C7—O1—C3—C2	−0.6 (7)	C14—C9—C10—C11	2.1 (8)
C7—O1—C3—C4	178.2 (4)	N2—C9—C10—C11	179.8 (4)
C1—C2—C3—O1	177.6 (5)	C9—C10—C11—C12	−3.0 (8)
C1—C2—C3—C4	−1.0 (7)	C10—C11—C12—C13	1.9 (9)
O1—C3—C4—N3	2.2 (6)	C10—C11—C12—Br1	−176.6 (4)
C2—C3—C4—N3	−178.9 (5)	C11—C12—C13—C14	0.1 (10)
O1—C3—C4—C5	−177.4 (4)	Br1—C12—C13—C14	178.6 (5)
C2—C3—C4—C5	1.5 (7)	C12—C13—C14—C9	−1.0 (10)
N3—C4—C5—C6	179.3 (5)	C10—C9—C14—C13	−0.1 (9)
C3—C4—C5—C6	−1.1 (7)	N2—C9—C14—C13	−177.6 (6)
C4—C5—C6—C1	0.3 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.88 (1)	2.38 (2)	3.228 (6)	163 (5)
N3—H3B···O1	0.88 (1)	2.28 (5)	2.628 (5)	103 (4)

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄BrN₃O
M_r	320.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	13.219 (2), 8.8289 (17), 13.506 (2)
β (°)	118.855 (6)
V (Å³)	1380.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.97
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART X2S benchtop
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.383, 0.755
No. of measured, independent and observed [I > 2Σ(I)] reflections	8299, 2408, 1775
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.198, 1.00
No. of reflections	2408
No. of parameters	178
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.98, −1.11

Computer programs: SMART X2S (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.876 (10)	2.38 (2)	3.228 (6)	163 (5)
N3—H3B···O1	0.879 (10)	2.28 (5)	2.628 (5)	103 (4)

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Acknowledgements

JAG thanks the American Crystallographic Association for a scholarship to the ACA summer school, and Bruce C. Noll of Bruker AXS Inc., and Peter Müller of the Massachusetts Institute of Technology for their assistance in this work.

References

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