1H-Benzotriazol-1-yl 4-{(E)-[4-(dimethyl­amino)­phen­yl]diazen­yl}benzoate

Abdelkrim El-Ghayoury; Leokadiya Zorina; Mostafa Khouili

doi:10.1107/S1600536813000846

. 2013 Jan 19;69(Pt 2):o262. doi: 10.1107/S1600536813000846

1H-Benzotriazol-1-yl 4-{(E)-[4-(dimethylamino)phenyl]diazenyl}benzoate

Abdelkrim El-Ghayoury ^a, Leokadiya Zorina ^b, Mostafa Khouili ^c,^*

PMCID: PMC3569792 PMID: 23424538

Abstract

The title compound, C₂₁H₁₈N₆O₂, was obtained as a by-product of a reaction between (E)-4-(4-dimethylaminophenylazo)benzoic acid and 2-amino-4-(2-pyridyl)-6-(6-pyridyl)-1,3,5-triazine, which has a very low solubility, under peptidic coupling conditions, using THF as solvent. The condensation reaction occurred between 1-hydroxybenzotriazole and (E)-4-(4-dimethylaminophenylazo)benzoic acid. The dihedral angle between the benzene rings in the (E)-diphenyldiazene fragment is 10.92 (13)° and that between the benzotriazole mean plane and the central benzene ring is 80.57 (7)°. In the crystal, π–π stacking [centroid–centroid distances = 3.823 (2) and 3.863 (2) Å] of similar fragments generates molecular layers parallel to (0-12). The crystal packing also features weak C—H⋯N hydrogen bonds involving N atoms of the benzotriazole ring.

Related literature

For applications of 1-hydroxybenzotriazole in organic syntheses, see: König & Geiger (1970 ▶); Miyazawa et al. (1984 ▶); Baldini et al. (2008 ▶). For the use of 1-hydroxybenzotriazole in the preparation of coordination compounds, see: Papaefstathiou et al. (2002 ▶). graphic file with name e-69-0o262-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₈N₆O₂
M _r = 386.41
Triclinic,
a = 6.6362 (8) Å
b = 11.384 (3) Å
c = 13.022 (3) Å
α = 99.64 (3)°
β = 103.61 (2)°
γ = 92.440 (17)°
V = 939.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Bruker KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.697, T _max = 0.746
18381 measured reflections
4288 independent reflections
2107 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.142
S = 1.04
4288 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DIRAX (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(21.3KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000846/zq2193sup1.cif

e-69-0o262-sup1.cif^{(21.3KB, cif)}

Click here for additional data file.^{(205.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000846/zq2193Isup2.hkl

e-69-0o262-Isup2.hkl^{(205.8KB, hkl)}

Click here for additional data file.^{(7.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000846/zq2193Isup3.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
C4—H4⋯N5ⁱ	0.93	2.63	3.415 (3)	142
C23—H23⋯N6ⁱⁱ	0.93	2.63	3.560 (3)	176

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

Acknowledgments

The authors acknowledge the CNRST (Morocco) for partial financial support

supplementary crystallographic information

Comment

1-Hydroxybenzotriazole is a widely used compound in organic syntheses to decrease the racemization in the carbodiimide peptide coupling (König et al., 1970) and especially in racemization-free condensation of aminoacids and peptidic fragments (Miyazawa et al., 1984). It has also been utilized to form a benzotriazolyl active ester (Baldini et al., 2008). Recently 1-hydroxybenzotriazole was used in the preparation of one-dimensional coordination polymers (Papaefstathiou et al., 2002).

The molecular structure of the title compound is shown in Fig. 1. The diphenyldiazene fragment of the molecule is not planar (its benzene rings form a dihedral angle of 10.92 (13) °) and adopts an E conformation about the N2═N3 bond. The benzotriazolyl fragment (tautomer A) is essentially planar with an r.m.s. deviation of 0.010 (2) Å and is almost perpendicularly attached to the benzoate ring. The dihedral angles between mean plane of benzotriazolyl and two benzene rings, C3–C8 & C9–C14, are 88.57 (7) ° and 80.57 (7) °, respectively.

In the crystal structure (Fig. 2) π-π stacking of the similar fragments generates molecular layers parallel to (012) [Cg1···Cg2ⁱ, 3.823 Å; Cg3···Cg3ⁱⁱ, 3.863 Å; Cg1, Cg2 and Cg3 are the centroids of the C3–C8, C9–C14 and C20–C25 rings, respectively; symmetry codes: (i) 1 + x, y, z; (ii) -3 - x, -1 - y, -1 - z]. Adjacent molecules inside and between the layers are linked additionally by weak C—H···N hydrogen bonds to N-atoms of the benzotriazolyl ring (the shortest H···N distances are 2.63 Å).

Experimental

The title compound, C₂₁H₁₈N₆O₂, was obtained as a byproduct of a reaction between (E)-4-(4-dimethylaminophenylazo)benzoic acid and 2-amino-4-(2-pyridyl)-6-(6-pyridyl)-1,3,5-triazine, which is hardly soluble, under peptidic coupling condition. The condensation reaction has occurred between 1-hydroxybenzotriazole and (E)-4-(4-dimethylaminophenylazo)benzoic acid.