4-[(4-Chloro­phen­yl)diazen­yl]-3-meth­oxy­aniline

Mohammad Kazem Rofouei; Zahra Ghalami; Jafar Attar Gharamaleki; Giuseppe Bruno; Hadi Amiri Rudbari

doi:10.1107/S160053681102472X

. 2011 Jun 30;67(Pt 7):o1852. doi: 10.1107/S160053681102472X

4-[(4-Chlorophenyl)diazenyl]-3-methoxyaniline

Mohammad Kazem Rofouei ^a,^*, Zahra Ghalami ^a, Jafar Attar Gharamaleki ^a, Giuseppe Bruno ^b, Hadi Amiri Rudbari ^b

PMCID: PMC3152038 PMID: 21837217

Abstract

The title compound, C₁₃H₁₂ClN₃O, exhibits a trans geometry about the N=N double bond in the solid state. The dihedral angle between the rings is 22.20 (8)°. Intermolecular N—H⋯O hydrogen bonds between the amine and methoxy groups lead to the formation of a chain-like polymer along the c axis with a C(6) graph set. There is also weak non-classical C—H⋯N hydrogen bonds involving an aromatic C—H group and a diazenyl N atom, which connect the chains into a two-dimensional framework.

Related literature

For applications of diazonium compounds, see: Patai (1978 ▶); Hunger et al. (2005 ▶). For the synthesis and crystal structures of Hg(II) and Cd(II) complexes with [1,3-bis(2-methoxyphenyl)]triazene, see: Rofouei, Hematyar et al. (2009 ▶); Rofouei, Melardi et al. (2009 ▶).

Experimental

Crystal data

C₁₃H₁₂ClN₃O
M _r = 261.71
Monoclinic,
a = 15.398 (2) Å
b = 12.132 (2) Å
c = 14.276 (2) Å
β = 107.65 (1)°
V = 2541.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.30 × 0.17 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.698, T _max = 0.746
42735 measured reflections
2778 independent reflections
2481 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.118
S = 1.04
2778 reflections
172 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; 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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102472X/bh2358sup1.cif

e-67-o1852-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102472X/bh2358Isup2.hkl

e-67-o1852-Isup2.hkl^{(133.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681102472X/bh2358Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Oⁱ	0.85 (2)	2.47 (2)	3.222 (2)	147 (2)
C12—H12⋯N3ⁱⁱ	0.93	2.62	3.379 (2)	140

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

Diazonium ions are present in solutions such as benzenediazonium chloride solution. They contain an -N₂⁺ group. For example in the case of benzenediazonium chloride, this is attached to a benzene ring. The most important application area of these compounds is organic synthesis of azo dyes (Patai, 1978; Hunger et al., 2005). Diazenyl compounds characterized by having a diazo group (—N═N—) commonly adopt the trans configuration in the ground state. We have previously reported the synthesis of Hg(II) and Cd(II) complexes with [1,3-bis(2-methoxyphenyl)]triazene (Rofouei, Hematyar, Ghoulipour & Gharamaleki, 2009; Rofouei, Melardi, Khalili, Ghaydari & Barkhi, 2009).

When attempting to prepare an asymmetric triazene compound using p-chloroaniline and m-anizidine, we instead obtained the title diazo compound, C₁₃H₁₂ClN₃O (Fig. 1). The molecule adopts the trans configuration and the C1—N3—N2—C7 dihedral angle is 175.50 (10)°. The C10—N1, C7—N2 and C1—N3 bond lengths are 1.3657 (19), 1.3985 (16) and 1.4206 (17) Å, respectively, consistent with single and double bonds between related C and N atoms. In the crystal lattice of the title compound, the molecules are linked into chain-like polymers along the c crystallographic axis, with C(6) graph set, through N1—H1A···O hydrogen bonds with D···A separations of 3.222 (2) Å (Fig. 2). There is also C12—H12···N3 non-classic hydrogen bonds with D···A distance of 3.379 (2) Å. The unit cell packing diagram of the title compound is shown in Fig. 3.

Experimental

To a 1000 ml flask in ice bath, was added 6.36 g (0.05 mol) of p-chloroaniline and 4.68 g (0.13 mol) of HCl (d = 1.18 g.ml^-1). To the obtained solution was added dropwise a solution of sodium nitrite (4.14 g in 25 ml H₂O). Then, a diluted solution of m-anizidine (6.15 g, 0.05 mol) in 10 ml of methanol was added to the solution. The pH of the solution was adjusted at about 7–8 by adding a solution of 14.76 g of sodium acetate (0.18 mol) in 45 ml H₂O as solvent. The solution was stirred for about 45 minutes, giving an orange precipitate. It was then filtered off and dried in vacuum. After dissolving in DMF and recrystallization, orange crystals of the title compound were obtained. M.p. 191–193 °C. Elemental Anal. calc. for C₁₃H₁₂ClN₃O: C 59.66, H 4.62, N 16.06 %; ound: C 59.79, H 4.24, N 15.85 %. ¹H-NMR (300 MHz, d₆-DMSO) δ, ppm: 3.85 (3H, CH₃), 6.19–7.69 (9H, aromatic and NH₂ groups). ¹³C-NMR 100 MHz, DMSO) δ, ppm: 55.4 (O—CH₃), 96.0–159.8 (C atoms of aromatic rings)