3-(2-Eth­oxy­phen­yl)-1-(3-nitro­phen­yl)triaz-1-ene

Mohammad Reza Melardi; Atefeh Ghannadan; Mitra Peyman; Giuseppe Bruno; Hadi Amiri Rudbari

doi:10.1107/S1600536811048781

. 2011 Nov 30;67(Pt 12):o3485. doi: 10.1107/S1600536811048781

3-(2-Ethoxyphenyl)-1-(3-nitrophenyl)triaz-1-ene

Mohammad Reza Melardi ^a,^*, Atefeh Ghannadan ^a, Mitra Peyman ^a, Giuseppe Bruno ^b, Hadi Amiri Rudbari ^b

PMCID: PMC3239109 PMID: 22199957

Abstract

The title compound, C₁₄H₁₄N₄O₃, exhibits a trans geometry about the N=N double bond in the triazene unit. The molecule is approximately planar (r.m.s. deviation = 0.044 Å for all non-H atoms). An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, C—H⋯N hydrogen bonds lead to the formation of dimers which are, in turn, connected to each other by C—H⋯O hydrogen bonds, forming infinite chains of R ₂ ²(8) graph-set motif.

Related literature

For aryl triazenes, their structural properties and metal complexes see: Meldola & Streatfield (1888 ▶); Leman et al. (1993 ▶); Chen et al. (2002 ▶); Vrieze & Van Koten (1987 ▶). For a similar structure with cyano instead of ethoxy groups, see: Melardi et al. (2008 ▶). For the synthesis and characterization of a similar structure with methoxy instead of ethoxy groups, see: Rofouei et al. (2006 ▶). For the synthesis and crystal structures of mercury(II) and silver(I) complexes with 1,3-bis(2-methoxyphenyl)triazene, see: Hematyar & Rofouei (2008 ▶) and Payehghadr et al. (2007 ▶), respectively. For hydrogen-bond patterns and related graph sets, see: Grell et al. (2002 ▶).

Experimental

Crystal data

C₁₄H₁₄N₄O₃
M _r = 286.29
Triclinic,
a = 6.7754 (4) Å
b = 7.5482 (4) Å
c = 14.0467 (7) Å
α = 99.057 (3)°
β = 102.479 (2)°
γ = 90.192 (3)°
V = 692.14 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.55 × 0.33 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.688, T _max = 0.746
26097 measured reflections
3178 independent reflections
2693 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.115
S = 1.06
3178 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 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/S1600536811048781/qm2042sup1.cif

e-67-o3485-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048781/qm2042Isup2.hkl

e-67-o3485-Isup2.hkl^{(152.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811048781/qm2042Isup3.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—H1⋯O1	0.86	2.26	2.6130 (12)	105
C7—H2A⋯O3ⁱ	0.97	2.55	3.4595 (18)	157
C10—H10⋯N3ⁱⁱ	0.93	2.65	3.543 (3)	161

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

supplementary crystallographic information

Comment

Aryl triazenes have been studied for over 130 years for their interesting structural, anticancer, and reactivity properties. The first extensive investigation of the coordination chemistry of a triazene derivative (1,3 diphenyltriazene) was carried out in 1887 by Meldola (Meldola et al., 1888). In the intervening years, numerous transition metal triazenide compounds have been studied (Leman et al., 1993). Triazene compounds characterized by having a diazoamino group commonly adopt a trans configuration in the ground state (Chen et al., 2002). The study of transition metal complexes containing 1,3-diaryltriazenide [RN═N—NR]- ligands has increased greatly in the past few years, because of their potential reactivity in relation to their several coordination modes (Vrieze et al., 1987). We have recently reported the synthesis and characterization of the two molecules 1,3-bis(2-methoxyphenyl)triazene (Rofouei, et al., 2006) and 1,3-bis(2-cyanophenyl)triazene (Melardi, et al., 2008).

The title compound, C₁₄H₁₄N₄O₃, is a related triazene compound. It exhibits a trans stereo chemistry of the N═N double bond, and the C9—N3—N2—N1 and C1—N1—N2—N3 torsion angles are -179.23 (9) and 177.91 (10)°, respectively which indicates the molecule is planar. The N1—N2 and N2—N3 bond distances are 1.3295 (13) and 1.2550 (14) Å, respectively, which indicates the presence of distinct single and double bonds between the nitrogen atoms. These values are in good agreement with the reported data for N—N and N═N bond distances (Hematyar, et al., 2008; Payehghadr, et al. 2007). For example, in 1,3-bis(2-cyanophenyl)triazene, the N—N and N═N bond distances are 1.335 (5) and 1.289 (5) Å (Melardi, et al., 2008). Individual molecules are mostly planar with an r.m.s. deviation from planarity of 0.044 Å for all non-hydrogen atoms. Every molecule in the molecular structure (Fig. 1) is connected to other unit by two distinct C—H···N hydrogen bonds to form dimers. The resultant dimers are then connected to each other by C—H···O hydrogen bonds to form infinite chains with R²₂(8) graph-set motifs (Grell et al., 2002)) (Fig. 2). Unit cell diagram of the title compound is illustrated in Fig. 3.

Experimental

The compound was prepared by the following method: A 100 ml flask was charged with 10 g of ice and 15 ml of water and then cooled to 273 k in an ice-bath. To this was added 2 mmol (0.344 g) of 3-nitroaniline and 2 mmol of hydrochloric acid (36.5%) and 2 ml of water. To thissolution was then added a solution containing NaNO₂ (2 mmol, 0.16 g) in 2 ml of water during a 15 min period. After mixing for 15 min, the obtained solution was added to a solution of 2 mmol (0.261 ml) of o-phenetidin and 2 ml of methanol and 2 ml of water.

After that a solution containing 36 mmol (2.95 g) of sodium acetate in 10 ml of water was added. After mixing for 24 h the orange product was filtered off and dissolved in DMSO. Recrystallization from DMSO afforded the product as an orange crystalline material. ¹H NMR (300MHZ, DMSO): 1.37(6H, CH₃), 4.12(4H, CH₂), 6.98–8.07 (8H, aromatic), 12.93(1H, NH). IR (KBr): 3326, 1484, 1468, 1253, 1046, 816 cm^-1