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

El-Ghayoury, A.; Zorina, L.; Khouili, M.

doi:10.1107/S1600536813000846

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o262

doi:10.1107/S1600536813000846

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

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

^aLUNAM Université, Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, CNRS-UMR 6200, 2 bd. Lavoisier, 49045 Angers, France, ^bInstitute of Solid State Physics, RAS, 142432 Chernogolovka MD, Russian Federation, and ^cLaboratoire de Chimie Organique et Analytique, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, BP 523, 23000 Beni-Mellal, Morocco
^*Correspondence e-mail: m.khouili@usms.ma

(Received 21 December 2012; accepted 9 January 2013; online 19 January 2013)

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 ).

Experimental

Crystal data

C₂₁H₁₈N₆O₂
M_r = 386.41
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.062
wR(F²) = 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

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
Symmetry codes: (i) -x+1, -y, -z+2; (ii) x+1, y, z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813000846/zq2193sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536813000846/zq2193Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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).

Experimental top

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.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound viewed along the a–axis. Hydrogen C—H···N bonds are shown as dashed lines.

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

Crystal data top

C₂₁H₁₈N₆O₂	Z = 2
M_r = 386.41	F(000) = 404
Triclinic, P1	D_x = 1.366 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6362 (8) Å	Cell parameters from 4814 reflections
b = 11.384 (3) Å	θ = 3.7–27.6°
c = 13.022 (3) Å	µ = 0.09 mm⁻¹
α = 99.64 (3)°	T = 293 K
β = 103.61 (2)°	Prism, dark-red
γ = 92.440 (17)°	0.3 × 0.2 × 0.2 mm
V = 939.2 (3) Å³

Data collection top

Bruker KappaCCD diffractometer	4288 independent reflections
Radiation source: fine-focus sealed tube	2107 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.059
Detector resolution: 9 pixels mm^-1	θ_max = 27.6°, θ_min = 3.7°
combined ω– and ϕ–scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −14→14
T_min = 0.697, T_max = 0.746	l = −16→16
18381 measured reflections

Refinement top

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)] = 0.062	Hydrogen site location: difference Fourier map
wR(F²) = 0.142	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0421P)² + 0.3933P] where P = (F_o² + 2F_c²)/3
4288 reflections	(Δ/σ)_max = 0.006
264 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₁H₁₈N₆O₂	γ = 92.440 (17)°
M_r = 386.41	V = 939.2 (3) Å³
Triclinic, P1	Z = 2
a = 6.6362 (8) Å	Mo Kα radiation
b = 11.384 (3) Å	µ = 0.09 mm⁻¹
c = 13.022 (3) Å	T = 293 K
α = 99.64 (3)°	0.3 × 0.2 × 0.2 mm
β = 103.61 (2)°

Data collection top

Bruker KappaCCD diffractometer	4288 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2107 reflections with I > 2σ(I)
T_min = 0.697, T_max = 0.746	R_int = 0.059
18381 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
4288 reflections	Δρ_min = −0.18 e Å⁻³
264 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.7674 (4)	0.3683 (3)	1.0813 (2)	0.0622 (8)
H1A	1.8814	0.4273	1.0911	0.093*
H1B	1.8198	0.2915	1.0858	0.093*
H1C	1.6942	0.3894	1.1362	0.093*
C2	1.7041 (4)	0.4217 (3)	0.9009 (2)	0.0616 (8)
H2A	1.8431	0.4572	0.9338	0.092*
H2B	1.6156	0.4828	0.8805	0.092*
H2C	1.7048	0.3639	0.8382	0.092*
C3	1.4360 (3)	0.3014 (2)	0.94775 (19)	0.0396 (6)
C4	1.3631 (4)	0.2398 (2)	1.0190 (2)	0.0424 (6)
H4	1.4470	0.2409	1.0874	0.051*
C5	1.3021 (4)	0.2962 (2)	0.8449 (2)	0.0481 (7)
H5	1.3452	0.3359	0.7958	0.058*
C6	1.1699 (4)	0.1782 (2)	0.9887 (2)	0.0439 (6)
H6	1.1252	0.1386	1.0373	0.053*
C7	1.1107 (4)	0.2342 (2)	0.8161 (2)	0.0479 (7)
H7	1.0259	0.2322	0.7478	0.057*
C8	1.0396 (3)	0.1736 (2)	0.8874 (2)	0.0421 (6)
C9	0.5372 (3)	0.0387 (2)	0.7486 (2)	0.0424 (6)
C10	0.4539 (3)	−0.0039 (2)	0.8252 (2)	0.0418 (6)
H10	0.5271	0.0114	0.8970	0.050*
C11	0.4233 (4)	0.0191 (2)	0.6422 (2)	0.0527 (7)
H11	0.4757	0.0504	0.5912	0.063*
C12	0.2630 (3)	−0.0688 (2)	0.7946 (2)	0.0421 (6)
H12	0.2079	−0.0973	0.8459	0.051*
C13	0.2336 (4)	−0.0462 (2)	0.6120 (2)	0.0516 (7)
H13	0.1591	−0.0600	0.5404	0.062*
C14	0.1516 (3)	−0.0921 (2)	0.6875 (2)	0.0405 (6)
C15	−0.0433 (4)	−0.1686 (2)	0.6479 (2)	0.0459 (6)
C20	−0.4479 (3)	−0.4709 (2)	0.64582 (19)	0.0422 (6)
C21	−0.2442 (3)	−0.4259 (2)	0.65840 (19)	0.0396 (6)
C22	−0.5059 (4)	−0.5924 (2)	0.6047 (2)	0.0531 (7)
H22	−0.6414	−0.6247	0.5956	0.064*
C23	−0.0905 (4)	−0.4947 (2)	0.6317 (2)	0.0517 (7)
H23	0.0451	−0.4627	0.6405	0.062*
C24	−0.3566 (5)	−0.6615 (2)	0.5784 (2)	0.0587 (8)
H24	−0.3908	−0.7426	0.5512	0.070*
C25	−0.1519 (4)	−0.6131 (3)	0.5914 (2)	0.0591 (8)
H25	−0.0548	−0.6633	0.5720	0.071*
N1	1.6270 (3)	0.36337 (19)	0.97666 (17)	0.0496 (6)
N2	0.8454 (3)	0.10799 (17)	0.86454 (18)	0.0453 (5)
N3	0.7346 (3)	0.10456 (18)	0.77031 (18)	0.0494 (6)
N4	−0.2534 (3)	−0.30838 (18)	0.69602 (17)	0.0480 (6)
N5	−0.4415 (3)	−0.2807 (2)	0.70813 (18)	0.0565 (6)
N6	−0.5633 (3)	−0.3798 (2)	0.67744 (17)	0.0551 (6)
O1	−0.1551 (3)	−0.19039 (18)	0.55969 (16)	0.0682 (6)
O2	−0.0874 (2)	−0.22242 (15)	0.73157 (14)	0.0527 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0443 (15)	0.076 (2)	0.0604 (19)	−0.0091 (14)	0.0009 (13)	0.0164 (16)
C2	0.0521 (16)	0.0671 (19)	0.067 (2)	−0.0110 (14)	0.0127 (14)	0.0212 (16)
C3	0.0386 (13)	0.0351 (13)	0.0433 (15)	0.0008 (10)	0.0074 (11)	0.0068 (11)
C4	0.0431 (14)	0.0460 (15)	0.0370 (14)	−0.0008 (11)	0.0073 (11)	0.0098 (12)
C5	0.0453 (15)	0.0531 (16)	0.0472 (16)	−0.0056 (12)	0.0082 (12)	0.0198 (13)
C6	0.0437 (14)	0.0479 (15)	0.0430 (16)	−0.0001 (11)	0.0141 (12)	0.0122 (12)
C7	0.0459 (15)	0.0501 (16)	0.0444 (16)	−0.0017 (12)	0.0015 (12)	0.0146 (13)
C8	0.0398 (13)	0.0386 (14)	0.0468 (16)	0.0004 (11)	0.0097 (11)	0.0075 (12)
C9	0.0405 (14)	0.0362 (14)	0.0487 (16)	−0.0021 (11)	0.0094 (12)	0.0068 (12)
C10	0.0419 (14)	0.0373 (14)	0.0406 (15)	0.0002 (11)	0.0039 (11)	0.0014 (12)
C11	0.0540 (16)	0.0581 (17)	0.0452 (17)	−0.0100 (13)	0.0104 (13)	0.0138 (14)
C12	0.0440 (14)	0.0382 (14)	0.0428 (16)	−0.0001 (11)	0.0101 (11)	0.0055 (12)
C13	0.0520 (16)	0.0558 (17)	0.0405 (16)	−0.0077 (13)	0.0010 (12)	0.0084 (13)
C14	0.0396 (13)	0.0334 (13)	0.0452 (16)	−0.0007 (10)	0.0065 (11)	0.0044 (12)
C15	0.0437 (15)	0.0435 (15)	0.0493 (17)	−0.0021 (12)	0.0102 (13)	0.0087 (13)
C20	0.0362 (13)	0.0580 (17)	0.0328 (14)	−0.0067 (12)	0.0087 (10)	0.0113 (12)
C21	0.0362 (13)	0.0451 (15)	0.0359 (14)	−0.0049 (11)	0.0063 (10)	0.0089 (12)
C22	0.0534 (16)	0.0613 (19)	0.0413 (16)	−0.0204 (14)	0.0083 (12)	0.0119 (14)
C23	0.0377 (14)	0.0608 (19)	0.0565 (18)	0.0011 (13)	0.0084 (12)	0.0160 (15)
C24	0.074 (2)	0.0464 (17)	0.0523 (18)	−0.0070 (15)	0.0094 (15)	0.0118 (14)
C25	0.0589 (18)	0.0575 (19)	0.0603 (19)	0.0110 (14)	0.0115 (14)	0.0120 (15)
N1	0.0416 (12)	0.0570 (14)	0.0483 (13)	−0.0109 (10)	0.0056 (10)	0.0157 (11)
N2	0.0389 (11)	0.0432 (12)	0.0513 (14)	−0.0021 (9)	0.0078 (10)	0.0076 (10)
N3	0.0427 (12)	0.0479 (13)	0.0537 (15)	−0.0060 (10)	0.0082 (10)	0.0063 (11)
N4	0.0376 (12)	0.0490 (14)	0.0528 (14)	−0.0105 (10)	0.0106 (10)	0.0007 (11)
N5	0.0465 (13)	0.0686 (16)	0.0533 (15)	0.0000 (12)	0.0184 (11)	0.0007 (12)
N6	0.0410 (12)	0.0723 (16)	0.0512 (14)	−0.0088 (12)	0.0177 (10)	0.0032 (12)
O1	0.0596 (12)	0.0825 (15)	0.0505 (13)	−0.0235 (10)	−0.0060 (10)	0.0137 (11)
O2	0.0494 (10)	0.0538 (11)	0.0474 (11)	−0.0177 (8)	0.0048 (8)	0.0041 (9)

Geometric parameters (Å, º) top

C1—N1	1.449 (3)	C11—C13	1.372 (3)
C1—H1A	0.9600	C11—H11	0.9300
C1—H1B	0.9600	C12—C14	1.391 (3)
C1—H1C	0.9600	C12—H12	0.9300
C2—N1	1.451 (3)	C13—C14	1.391 (3)
C2—H2A	0.9600	C13—H13	0.9300
C2—H2B	0.9600	C14—C15	1.461 (3)
C2—H2C	0.9600	C15—O1	1.191 (3)
C3—N1	1.362 (3)	C15—O2	1.417 (3)
C3—C4	1.410 (3)	C20—N6	1.380 (3)
C3—C5	1.413 (3)	C20—C21	1.388 (3)
C4—C6	1.372 (3)	C20—C22	1.399 (3)
C4—H4	0.9300	C21—N4	1.354 (3)
C5—C7	1.365 (3)	C21—C23	1.385 (3)
C5—H5	0.9300	C22—C24	1.362 (4)
C6—C8	1.389 (3)	C22—H22	0.9300
C6—H6	0.9300	C23—C25	1.369 (4)
C7—C8	1.396 (3)	C23—H23	0.9300
C7—H7	0.9300	C24—C25	1.405 (4)
C8—N2	1.404 (3)	C24—H24	0.9300
C9—C11	1.389 (3)	C25—H25	0.9300
C9—C10	1.392 (3)	N2—N3	1.267 (3)
C9—N3	1.425 (3)	N4—N5	1.339 (3)
C10—C12	1.376 (3)	N4—O2	1.379 (2)
C10—H10	0.9300	N5—N6	1.306 (3)

N1—C1—H1A	109.5	C10—C12—H12	119.7
N1—C1—H1B	109.5	C14—C12—H12	119.7
H1A—C1—H1B	109.5	C11—C13—C14	120.6 (2)
N1—C1—H1C	109.5	C11—C13—H13	119.7
H1A—C1—H1C	109.5	C14—C13—H13	119.7
H1B—C1—H1C	109.5	C13—C14—C12	119.0 (2)
N1—C2—H2A	109.5	C13—C14—C15	117.4 (2)
N1—C2—H2B	109.5	C12—C14—C15	123.6 (2)
H2A—C2—H2B	109.5	O1—C15—O2	120.9 (2)
N1—C2—H2C	109.5	O1—C15—C14	129.1 (2)
H2A—C2—H2C	109.5	O2—C15—C14	110.0 (2)
H2B—C2—H2C	109.5	N6—C20—C21	109.7 (2)
N1—C3—C4	121.6 (2)	N6—C20—C22	130.7 (2)
N1—C3—C5	121.3 (2)	C21—C20—C22	119.6 (2)
C4—C3—C5	117.1 (2)	N4—C21—C23	134.8 (2)
C6—C4—C3	120.8 (2)	N4—C21—C20	101.5 (2)
C6—C4—H4	119.6	C23—C21—C20	123.7 (2)
C3—C4—H4	119.6	C24—C22—C20	117.5 (2)
C7—C5—C3	121.2 (2)	C24—C22—H22	121.3
C7—C5—H5	119.4	C20—C22—H22	121.3
C3—C5—H5	119.4	C25—C23—C21	115.4 (2)
C4—C6—C8	121.7 (2)	C25—C23—H23	122.3
C4—C6—H6	119.2	C21—C23—H23	122.3
C8—C6—H6	119.2	C22—C24—C25	121.6 (3)
C5—C7—C8	121.3 (2)	C22—C24—H24	119.2
C5—C7—H7	119.4	C25—C24—H24	119.2
C8—C7—H7	119.4	C23—C25—C24	122.3 (3)
C6—C8—C7	117.9 (2)	C23—C25—H25	118.9
C6—C8—N2	117.1 (2)	C24—C25—H25	118.9
C7—C8—N2	125.0 (2)	C3—N1—C1	122.1 (2)
C11—C9—C10	119.6 (2)	C3—N1—C2	121.0 (2)
C11—C9—N3	115.5 (2)	C1—N1—C2	116.8 (2)
C10—C9—N3	124.9 (2)	N3—N2—C8	114.5 (2)
C12—C10—C9	119.8 (2)	N2—N3—C9	113.9 (2)
C12—C10—H10	120.1	N5—N4—C21	113.82 (19)
C9—C10—H10	120.1	N5—N4—O2	119.6 (2)
C13—C11—C9	120.2 (2)	C21—N4—O2	126.21 (19)
C13—C11—H11	119.9	N6—N5—N4	106.8 (2)
C9—C11—H11	119.9	N5—N6—C20	108.21 (19)
C10—C12—C14	120.7 (2)	N4—O2—C15	112.84 (18)

N1—C3—C4—C6	179.7 (2)	C21—C20—C22—C24	−0.1 (4)
C5—C3—C4—C6	−0.2 (3)	N4—C21—C23—C25	−177.4 (3)
N1—C3—C5—C7	−179.9 (2)	C20—C21—C23—C25	−0.2 (4)
C4—C3—C5—C7	0.0 (4)	C20—C22—C24—C25	−0.3 (4)
C3—C4—C6—C8	0.3 (4)	C21—C23—C25—C24	−0.2 (4)
C3—C5—C7—C8	0.1 (4)	C22—C24—C25—C23	0.5 (4)
C4—C6—C8—C7	−0.1 (4)	C4—C3—N1—C1	0.9 (4)
C4—C6—C8—N2	179.9 (2)	C5—C3—N1—C1	−179.2 (2)
C5—C7—C8—C6	−0.1 (4)	C4—C3—N1—C2	177.1 (2)
C5—C7—C8—N2	179.9 (2)	C5—C3—N1—C2	−3.0 (4)
C11—C9—C10—C12	2.3 (4)	C6—C8—N2—N3	−178.6 (2)
N3—C9—C10—C12	−178.6 (2)	C7—C8—N2—N3	1.5 (3)
C10—C9—C11—C13	−2.7 (4)	C8—N2—N3—C9	−179.39 (19)
N3—C9—C11—C13	178.2 (2)	C11—C9—N3—N2	−171.6 (2)
C9—C10—C12—C14	−0.2 (3)	C10—C9—N3—N2	9.4 (3)
C9—C11—C13—C14	0.9 (4)	C23—C21—N4—N5	178.5 (3)
C11—C13—C14—C12	1.2 (4)	C20—C21—N4—N5	0.9 (3)
C11—C13—C14—C15	−175.3 (2)	C23—C21—N4—O2	−8.5 (4)
C10—C12—C14—C13	−1.6 (3)	C20—C21—N4—O2	173.9 (2)
C10—C12—C14—C15	174.7 (2)	C21—N4—N5—N6	−0.7 (3)
C13—C14—C15—O1	−7.1 (4)	O2—N4—N5—N6	−174.2 (2)
C12—C14—C15—O1	176.5 (3)	N4—N5—N6—C20	0.1 (3)
C13—C14—C15—O2	170.8 (2)	C21—C20—N6—N5	0.5 (3)
C12—C14—C15—O2	−5.6 (3)	C22—C20—N6—N5	−178.6 (2)
N6—C20—C21—N4	−0.8 (3)	N5—N4—O2—C15	−99.1 (3)
C22—C20—C21—N4	178.3 (2)	C21—N4—O2—C15	88.3 (3)
N6—C20—C21—C23	−178.8 (2)	O1—C15—O2—N4	6.6 (3)
C22—C20—C21—C23	0.4 (4)	C14—C15—O2—N4	−171.51 (18)
N6—C20—C22—C24	178.8 (3)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₈N₆O₂
M_r	386.41
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.6362 (8), 11.384 (3), 13.022 (3)
α, β, γ (°)	99.64 (3), 103.61 (2), 92.440 (17)
V (Å³)	939.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Bruker KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.697, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	18381, 4288, 2107
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.142, 1.04
No. of reflections	4288
No. of parameters	264
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: COLLECT (Hooft, 1998), DIRAX (Duisenberg, 1992), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N5ⁱ	0.93	2.63	3.415 (3)	142.0
C23—H23···N6ⁱⁱ	0.93	2.63	3.560 (3)	175.9

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x+1, y, z.

Acknowledgements

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

References

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