4-[(4-Bromo-phen-yl)diazen-yl]-2-eth-oxy-aniline.

The title compound, C(14)H(14)BrN(3)O, exhibits a trans geometry about the -N=N- double bond. The dihedral angle between the benzene rings is 24.01 (5)°. An intra-molecular N-H⋯O hydrogen bond occurs. In the crystal, inter-molecular 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 = 320.19

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.198

S = 1.00

2408 reflections

178 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.98 e Å−3

Δρmin = −1.11 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681104877X/pv2476sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104877X/pv2476Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681104877X/pv2476Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H14BrN3O	F(000) = 648
Mr = 320.19	Dx = 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

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

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(Fo2) + (0.1373P)2] where P = (Fo2 + 2Fc2)/3
2408 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.98 e Å−3
2 restraints	Δρmin = −1.11 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) .