1-(3,5-Dichloro­phen­yl)-3-(2-meth­oxy­phen­yl)triaz-1-ene

Mohammad Reza Melardi; Maryam Aghamohamadi; Jafar Attar Gharamaleki; Mohammad Kazem Rofouei; Behrouz Notash

doi:10.1107/S1600536812005132

. 2012 Feb 17;68(Pt 3):o724. doi: 10.1107/S1600536812005132

1-(3,5-Dichlorophenyl)-3-(2-methoxyphenyl)triaz-1-ene

Mohammad Reza Melardi ^a, Maryam Aghamohamadi ^a, Jafar Attar Gharamaleki ^b,^*, Mohammad Kazem Rofouei ^b, Behrouz Notash ^c

PMCID: PMC3295495 PMID: 22412606

Abstract

The title molecule, C₁₃H₁₁Cl₂N₃O, is almost planar and adopts a trans conformation with respect to the –N=N– bond; the dihedral angle between the rings is 3.47 (2)°. The N—N bond lengths indicate the presence of single- and double-bond characters and hence the –N=N—NH– moiety. In the crystal, inversion dimers linked by pairs of N—H⋯Cl hydrogen bonds occur, and C—H⋯π and π–π stacking interactions are also observed.

Related literature

For background literature and the synthesis of related compounds, see: Rofouei et al. (2009 ▶). For the synthesis and molecular structure of a similar monochloro-substituted triazene, see: Rofouei et al. (2012 ▶).

Experimental

Crystal data

C₁₃H₁₁Cl₂N₃O
M _r = 296.15
Monoclinic,
a = 15.422 (3) Å
b = 23.068 (5) Å
c = 7.6141 (15) Å
β = 92.60 (3)°
V = 2706.0 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 298 K
0.5 × 0.3 × 0.15 mm

Data collection

Stoe IPDS 2T diffractometer
15133 measured reflections
3659 independent reflections
2178 reflections with I > 2σ(I)
R _int = 0.162

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.137
S = 1.07
3659 reflections
177 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812005132/pv2511sup1.cif

e-68-0o724-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005132/pv2511Isup2.hkl

e-68-0o724-Isup2.hkl^{(179.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812005132/pv2511Isup3.cml

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

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

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1ⁱ	0.85 (2)	2.69 (2)	3.529 (2)	170 (3)
C1—H1C⋯Cg1ⁱⁱ	0.96	2.76	3.553 (4)	140

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

supplementary crystallographic information

Comment

In continuation of our studies on the synthesis and characterization of trizene compounds as ligands in our laboratory (Rofouei et al., 2012; Rofouei et al., 2009), we now report the crystal structure of the title compound.

The title molecule (Fig. 1) adopts trans configuration about the (–N2═N3–) bond and is almost planar with the dihedral angel between two aromatic rings 3.47 (2) °. Non-Classic N—H···Cl hydrogen bond with D···A distance of 3.529 (2) Å connect the individual molecules into dimers. The N1—N2 and N2—N3 bond distances are 1.323 (3) and 1.256 (3) Å, which indicate the presence of a single and a double bond characters, respectively. Another interesting feature of the title compound is the presence of π–π [Cg1···Cg1 distance of 3.757 (2) Å] and edge-to-face C1—H1C···Cg1 stacking interactions between the methoxy hydrogen and the phenyl ring with H···π distance of 2.76 Å, in which Cg1 is the center of (C2—C7) ring. Unit cell packing diagram of the title compound is presented in Fig. 2, showing N—H···Cl hydrogen bonds.

The bond distances and bond angles in the title compoiund are in agreement with the corresponding bond distances and bond angles reported for a closely related structure, [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazene (Rofouei et al., 2012).

Experimental

To a 1 L flask in an ice bath, was added dichloroaniline (6.36 g, 0.05 mol) and HCl (4.68 g, 0.13 mol; 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 o-anisidine (6.15 g, 0.05 mol) in methanol (10 ml) was added to the solution. The pH of the solution was adjusted at about 7–8 by adding a solution of sodium acetate ( 14.76 g, 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 under vacuum. After dissolving in dichloromethane and recrystallization, orange crystals of the title compound were obtained.