N-Paranitrophénylhydrazono-α-(2-méthyl­benzimidazol-1-yl)glyoxylate d'éthyle

Boudina, A.; Baouid, A.; Driss, M.; Soumhi, E.H.

doi:10.1107/S1600536811022148

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| juillet 2011| Page o1569

doi:10.1107/S1600536811022148

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N-Paranitrophénylhydrazono-α-(2-méthylbenzimidazol-1-yl)glyoxylate d'éthyle

Aicha Boudina,^a Abdesselam Baouid,^a Mohamed Driss ^b et El Hassane Soumhi ^c ^*

^aÉquipe de Chimie des Hétérocycles et Valorisation des Éxtraits des Plantes, Faculté des Sciences-Semlalia, Université Cadi Ayyad, Boulevard Abdelkrim Khattabi, BP 2390, 40001 Marrakech, Maroc, ^bLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 El Manar II Tunis, Tunisie, et ^cÉquipe de Chimie des Matériaux et de l'Environnement, FSTG-Marrakech, Université Cadi Ayyad, Boulevard Abdelkrim Khattabi, BP 549, Marrakech, Maroc
^*Courier électronique: eh_soumhi@yahoo.fr

(Reçu le 6 juin 2011; accepté le 7 juin 2011; online 11 juin 2011)

There are two independent molecules in the asymmetric unit of the title compound {systematic name: ethyl 2-(2-methyl-1H-benzimidazol-1-yl)-2-[2-(4-nitrophenyl)hydrazinylidene]ethanoate}, C₁₈H₁₇N₅O₄. Each molecule and its inversion-related partner are linked by a pair of intermolecular N—H⋯N hydrogen bonds, forming inversion dimers in the crystal structure.

Littérature associée

Pour le contexte général des derivées des benzodiazépines et benzotriazépines, voir: Bellantuono et al. (1980 ); Bartsch & Erker (1988 ); Baouid et al. (1994 , 1996 ); Jalal et al. (2002 ); Rossi et al. (1960 ). Pour structures associées, voir: Chiaroni et al. (1995 ); El Hazazi et al. (2000 ).

Partie expérimentale

Données cristallines

C₁₈H₁₇N₅O₄
M_r = 367,37
Triclinique, $[P \overline 1]$
a = 8,269 (3) Å
b = 11,523 (2) Å
c = 19,853 (6) Å
α = 87,44 (2)°
β = 80,67 (3)°
γ = 76,80 (2)°
V = 1817,3 (9) Å³
Z = 4
Radiation Mo Kα
μ = 0,10 mm⁻¹
T = 300 K
0,4 × 0,18 × 0,12 mm

Collection des données

Diffractomètre Enraf–Nonius CAD-4
9121 réflexions mesurées
7912 réflexions indépendantes
4441 réflexions avec I > 2σ(I)
R_int = 0,018
2 réflexions de référence chaque 60 min diminution d'intensité: 1,0%

Affinement

R[F² > 2σ(F²)] = 0,043
wR(F²) = 0,131
S = 1,01
7912 réflexions
492 paramètres
Paramètres des atomes H contraints
Δρ_max = 0,17 e Å⁻³
Δρ_min = −0,19 e Å⁻³

Tableau 1
Géometrie des liaisons hydrogène (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN2⋯N5ⁱ	0,86	2,19	2,954 (2)	148
N7—HN7⋯N10ⁱⁱ	0,86	2,19	2,967 (2)	150
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+2, -z.

Collection des données: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); affinement des paramètres de la maille: CAD-4 EXPRESS; réduction des données: MolEN (Fair, 1990 ); programme(s) pour la solution de la structure: SHELXS97 (Sheldrick, 2008 ); programme(s) pour l'affinement de la structure: SHELXL97 (Sheldrick, 2008); graphisme moléculaire: ORTEP-3 for Windows (Farrugia, 1997 ); logiciel utilisé pour préparer le matériel pour publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022148/is2730sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022148/is2730Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022148/is2730Isup3.cml

checkCIF report

Comment top

Les composés présentant un hétérocycle de différente taille accolé à un autre hétérocycle azoté à sept chaînons révélaient dans certains cas des propriétés pharmacologiques remarquables (Bellantuono et al., 1980; Bartsch & Erker, 1988). Dans ce contexte, notre équipe de recherche s'est intéressée à la synthèse de nouvelles molécules dérivées des benzodiazépines et benzotriazépines possédant des structures homologues à des composés biologiquement actifs (Baouid et al., 1996; El Hazazi et al., 2000; Jalal et al., 2002).

Développant ce travail, nous avons examiné le comportement de la [1,2,4]triazolo [4,3-a][1,5]benzodiazépine 1 (Baouid et al., 1994) vis-à-vis de α,α,α-trichloroéthane avec le diméthylformamide (DMF) moyennant le Mg-Barbier. L'objectif de cette réaction est la formation des aziridines polysubstitués à partir de l'imine et le α,α,α-trichloroéthane. Alors un produit inattendu est obtenu (Fig. 1). La réaction est effectuée dans le DMF, à une température comprise entre 5°C et 15 °C. Opérant avec un équivalent de DMF et la solution de trichloroéthane en présence de Mg-Barbier, on obtient après agitation du mélange réactionnel pendant une journée, le produit 2 avec un rendement de 60%. Dans cette réaction le DMF joue le rôle du catalyseur et de solvant puisque aucune réaction n'a eu lieu dans le diéthyléther ou dans le tétrahydrofurane (THF) au lieu de DMF.

L'évolution de la réaction a été suivie par la chromatographie sous couche mince (CCM). La formation du composé 2 s'explique vraisemblablement par un réarrangement sigmatropique-1,3 du cycle à sept éléments (Rossi et al., 1960), suivie de la perte du styrène aboutissant à un intermédiaire très instable qui se transpose à son tour pour conduire au produit réarrangé 2.

L'étude cristallographique a permis de déterminer clairement la stéréochimie du produit 2 (Fig. 2) et confirme ainsi le réarrangement du cycle à sept éléments suivi de la perte du styréne. La structure de ce composé, objet d'étude, cristallise dans le systéme triclinique, groupe d'espace P1, avec les paramètres de maille suivants: a = 8.269 (3) Å; b = 11.523 (2) Å; c = 19.853 (6) Å. L'unité asymétrique est formée de deux molécules cristallographiquement indépendantes A et B de formule identique: C₁₈H₁₇N₅O₄. Dans chaque molécule,le cycle 1–3,benzodiazole est pratiquement plan et présente un écart á la planéité de 0.0164 Å dans la molécule A et de 0.0098 Å dans B. Les caractéristiques géométriques de ce composé restent en bon accord avec celles observées dans d'autres composés simulaires (Chiaroni et al., 1995; El Hazazi et al., 2000).

Related literature top

Pour le contexte général des derivées des benzodiazépines et benzotriazépines, voir: Bellantuono et al. (1980); Bartsch & Erker (1988); Baouid et al. (1994, 1996); Jalal et al. (2002); Rossi et al. (1960). Pour structures associées, voir: Chiaroni et al. (1995); El Hazazi et al. (2000).

Experimental top

La réaction est effectuée dans les conditions de Mg-Barbier en présence de DMF. Le magnésium (5,4 mmoles) est suspendu dans 40 ml de DMF dans un ballon tricol muni d'un thermomètre et d'une ampoule à brome, et refroidie à une température T < 5 °C. La moitié de la solution contenant le monocycloadduit 1 (0,54 mmoles), le α,α,α-trichloroéthane (0,65 mmoles) et DMF (5 ml) est ajouté rapidement au mélange réactionnel. Le reste du réactant est additionné durant 5 min, puis la réaction est agitée fortement et elle est suivie par chromatographie sur couche mince jusqu'à la consommation complète du monocycloadduit 1. Après traitement habituel du mélange réactionnel, le résidu obtenu est chromatographié sur colonne de gel de silice puis recristallisé dans l'acétate d'éthyle pour isoler le produit 2. Ce composé est obtenu avec un rendement de 60%. Solide beige; P.F. 201–202 °C.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: MolEN (Fair, 1990); 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).

Figures top

	Fig. 1. Schéma réactionnel du composé étudié.
	Fig. 2. Représentation ORTEP de la structure avec les spheères d'atomes à 50% de probabilité.

Ethyl 2-(2-methyl-1H-benzimidazol-1-yl)-2-[2-(4- nitrophenyl)hydrazinylidene]ethanoate top

Crystal data top

C₁₈H₁₇N₅O₄	Z = 4
M_r = 367.37	F(000) = 768
Triclinic, P1	D_x = 1.343 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.269 (3) Å	Cell parameters from 25 reflections
b = 11.523 (2) Å	θ = 10–15°
c = 19.853 (6) Å	µ = 0.10 mm⁻¹
α = 87.44 (2)°	T = 300 K
β = 80.67 (3)°	Plate, yellow
γ = 76.80 (2)°	0.4 × 0.18 × 0.12 mm
V = 1817.3 (9) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.018
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 1.8°
Graphite monochromator	h = −10→10
ω/2θ scans	k = −1→14
9121 measured reflections	l = −25→25
7912 independent reflections	2 standard reflections every 60 min
4441 reflections with I > 2σ(I)	intensity decay: 1.0%

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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F²) = 0.131	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0566P)² + 0.2299P] where P = (F_o² + 2F_c²)/3
7912 reflections	(Δ/σ)_max < 0.001
492 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₈H₁₇N₅O₄	γ = 76.80 (2)°
M_r = 367.37	V = 1817.3 (9) Å³
Triclinic, P1	Z = 4
a = 8.269 (3) Å	Mo Kα radiation
b = 11.523 (2) Å	µ = 0.10 mm⁻¹
c = 19.853 (6) Å	T = 300 K
α = 87.44 (2)°	0.4 × 0.18 × 0.12 mm
β = 80.67 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.018
9121 measured reflections	2 standard reflections every 60 min
7912 independent reflections	intensity decay: 1.0%
4441 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
7912 reflections	Δρ_min = −0.19 e Å⁻³
492 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
O1	1.1114 (2)	−0.22059 (13)	0.65166 (8)	0.0725 (4)
O2	1.0965 (2)	−0.08283 (15)	0.72248 (9)	0.0889 (6)
O3	0.3711 (2)	0.25412 (13)	0.32862 (8)	0.0678 (4)
O4	0.54009 (18)	0.07952 (12)	0.35251 (7)	0.0590 (4)
N1	1.0594 (2)	−0.11839 (15)	0.67144 (9)	0.0553 (4)
N2	0.64051 (19)	0.20284 (12)	0.51891 (8)	0.0474 (4)
HN2	0.6036	0.2757	0.5317	0.057*
N3	0.59856 (19)	0.16436 (12)	0.46301 (8)	0.0444 (4)
N4	0.41859 (18)	0.35473 (12)	0.44852 (7)	0.0415 (3)
N5	0.33720 (19)	0.55351 (12)	0.44995 (8)	0.0486 (4)
C1	0.9503 (2)	−0.03414 (16)	0.63150 (9)	0.0455 (4)
C2	0.8921 (2)	−0.07698 (16)	0.57840 (9)	0.0498 (5)
H2	0.9224	−0.1578	0.5683	0.060*
C3	0.7888 (2)	0.00099 (15)	0.54058 (10)	0.0479 (4)
H3	0.7481	−0.0270	0.5049	0.058*
C4	0.7457 (2)	0.12177 (14)	0.55599 (9)	0.0418 (4)
C5	0.8045 (3)	0.16319 (16)	0.60991 (10)	0.0541 (5)
H5	0.7750	0.2440	0.6202	0.065*
C6	0.9061 (3)	0.08517 (17)	0.64807 (11)	0.0557 (5)
H6	0.9446	0.1124	0.6846	0.067*
C7	0.5006 (2)	0.23631 (15)	0.42798 (9)	0.0426 (4)
C8	0.4626 (2)	0.19271 (17)	0.36421 (10)	0.0478 (4)
C9	0.5146 (3)	0.0271 (2)	0.29101 (11)	0.0681 (6)
H9A	0.5655	0.0643	0.2508	0.082*
H9B	0.3955	0.0378	0.2894	0.082*
C10	0.5964 (3)	−0.1029 (2)	0.29373 (13)	0.0821 (8)
H10A	0.5840	−0.1412	0.2535	0.098*
H10B	0.5439	−0.1386	0.3334	0.098*
H10C	0.7138	−0.1121	0.2960	0.098*
C11	0.2933 (2)	0.38263 (15)	0.50564 (9)	0.0425 (4)
C12	0.2219 (2)	0.31282 (17)	0.55511 (10)	0.0518 (5)
H12	0.2577	0.2302	0.5555	0.062*
C13	0.0942 (3)	0.3723 (2)	0.60408 (11)	0.0611 (5)
H13	0.0434	0.3285	0.6382	0.073*
C14	0.0407 (3)	0.4952 (2)	0.60341 (11)	0.0638 (6)
H14	−0.0462	0.5321	0.6367	0.077*
C15	0.1138 (3)	0.56380 (19)	0.55427 (11)	0.0581 (5)
H15	0.0773	0.6464	0.5540	0.070*
C16	0.2435 (2)	0.50651 (15)	0.50501 (10)	0.0449 (4)
C17	0.4368 (2)	0.46180 (15)	0.41703 (9)	0.0433 (4)
C18	0.5558 (3)	0.46803 (18)	0.35304 (10)	0.0565 (5)
H18A	0.5017	0.4618	0.3145	0.068*
H18B	0.6530	0.4037	0.3524	0.068*
H18C	0.5896	0.5426	0.3509	0.068*
O5	0.7356 (3)	0.28956 (17)	−0.17974 (11)	0.1057 (7)
O6	0.7618 (2)	0.43406 (17)	−0.25022 (9)	0.0879 (5)
O7	−0.25402 (19)	0.73598 (13)	0.15264 (8)	0.0698 (4)
O8	−0.04397 (17)	0.57184 (12)	0.14022 (7)	0.0583 (4)
N6	0.6970 (2)	0.39426 (18)	−0.19733 (11)	0.0673 (5)
N7	0.1779 (2)	0.70257 (13)	−0.03046 (8)	0.0512 (4)
HN7	0.1503	0.7765	−0.0418	0.061*
N8	0.0946 (2)	0.65968 (13)	0.02521 (8)	0.0482 (4)
N9	−0.10387 (19)	0.84754 (13)	0.04199 (8)	0.0466 (4)
N10	−0.2019 (2)	1.04477 (14)	0.05012 (9)	0.0562 (4)
C19	0.5655 (2)	0.47559 (17)	−0.15198 (10)	0.0507 (5)
C20	0.4804 (3)	0.42932 (18)	−0.09549 (11)	0.0580 (5)
H20	0.5092	0.3484	−0.0853	0.069 (6)*
C21	0.3523 (3)	0.50385 (17)	−0.05419 (10)	0.0542 (5)
H21	0.2941	0.4732	−0.0161	0.065*
C22	0.3101 (2)	0.62482 (15)	−0.06951 (9)	0.0435 (4)
C23	0.3984 (2)	0.66996 (17)	−0.12683 (10)	0.0532 (5)
H23	0.3711	0.7510	−0.1370	0.064*
C24	0.5258 (2)	0.59540 (18)	−0.16848 (10)	0.0544 (5)
H24	0.5840	0.6252	−0.2069	0.065*
C25	−0.0334 (2)	0.72821 (16)	0.06040 (9)	0.0468 (4)
C26	−0.1234 (3)	0.68024 (17)	0.12275 (10)	0.0505 (5)
C27	−0.1237 (3)	0.52064 (19)	0.20149 (10)	0.0628 (6)
H27A	−0.2407	0.5242	0.1986	0.075*
H27B	−0.1191	0.5646	0.2414	0.075*
C28	−0.0312 (3)	0.3948 (2)	0.20676 (13)	0.0821 (7)
H28A	0.0850	0.3923	0.2082	0.098*
H28B	−0.0399	0.3515	0.1678	0.098*
H28C	−0.0788	0.3593	0.2476	0.098*
C29	−0.1922 (2)	0.88137 (17)	−0.01301 (10)	0.0495 (5)
C30	−0.2235 (3)	0.8165 (2)	−0.06471 (11)	0.0635 (6)
H30	−0.1833	0.7344	−0.0680	0.076*
C31	−0.3176 (3)	0.8807 (3)	−0.11099 (13)	0.0794 (7)
H31	−0.3396	0.8408	−0.1470	0.095*
C32	−0.3802 (3)	1.0024 (3)	−0.10548 (15)	0.0858 (8)
H32	−0.4443	1.0421	−0.1374	0.103*
C33	−0.3497 (3)	1.0659 (2)	−0.05372 (14)	0.0732 (7)
H33	−0.3930	1.1477	−0.0502	0.088*
C34	−0.2524 (2)	1.00450 (18)	−0.00674 (11)	0.0547 (5)
C35	−0.1178 (2)	0.95001 (17)	0.07824 (10)	0.0491 (5)
C36	−0.0474 (3)	0.9487 (2)	0.14211 (11)	0.0652 (6)
H36A	−0.0272	1.0258	0.1490	0.078*
H36B	0.0565	0.8899	0.1390	0.078*
H36C	−0.1257	0.9296	0.1798	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0922 (12)	0.0459 (9)	0.0725 (10)	0.0069 (8)	−0.0251 (9)	0.0030 (7)
O2	0.1183 (15)	0.0768 (11)	0.0719 (11)	0.0034 (10)	−0.0501 (10)	−0.0072 (9)
O3	0.0838 (11)	0.0588 (9)	0.0641 (9)	−0.0081 (8)	−0.0328 (8)	0.0002 (7)
O4	0.0719 (9)	0.0507 (8)	0.0512 (8)	−0.0031 (7)	−0.0112 (7)	−0.0159 (6)
N1	0.0613 (10)	0.0521 (10)	0.0494 (10)	−0.0047 (8)	−0.0121 (8)	0.0042 (8)
N2	0.0582 (10)	0.0301 (7)	0.0543 (9)	−0.0046 (7)	−0.0170 (8)	−0.0029 (7)
N3	0.0513 (9)	0.0366 (8)	0.0456 (8)	−0.0085 (7)	−0.0100 (7)	−0.0019 (7)
N4	0.0456 (8)	0.0331 (7)	0.0457 (8)	−0.0070 (6)	−0.0096 (7)	0.0008 (6)
N5	0.0521 (9)	0.0340 (8)	0.0625 (10)	−0.0073 (7)	−0.0216 (8)	0.0026 (7)
C1	0.0487 (10)	0.0400 (10)	0.0456 (10)	−0.0055 (8)	−0.0085 (8)	0.0039 (8)
C2	0.0616 (12)	0.0337 (9)	0.0503 (11)	−0.0034 (9)	−0.0076 (9)	−0.0020 (8)
C3	0.0607 (12)	0.0352 (9)	0.0486 (10)	−0.0071 (8)	−0.0155 (9)	−0.0023 (8)
C4	0.0445 (10)	0.0335 (9)	0.0472 (10)	−0.0086 (7)	−0.0076 (8)	0.0015 (7)
C5	0.0680 (13)	0.0328 (9)	0.0643 (13)	−0.0080 (9)	−0.0216 (10)	−0.0052 (9)
C6	0.0648 (13)	0.0459 (11)	0.0614 (13)	−0.0106 (10)	−0.0260 (10)	−0.0049 (9)
C7	0.0460 (10)	0.0353 (9)	0.0452 (10)	−0.0070 (8)	−0.0064 (8)	0.0005 (8)
C8	0.0528 (11)	0.0451 (11)	0.0455 (10)	−0.0109 (9)	−0.0076 (9)	0.0002 (8)
C9	0.0759 (15)	0.0747 (15)	0.0537 (13)	−0.0151 (12)	−0.0054 (11)	−0.0255 (11)
C10	0.103 (2)	0.0704 (16)	0.0693 (15)	−0.0232 (14)	0.0110 (14)	−0.0295 (13)
C11	0.0440 (10)	0.0400 (9)	0.0451 (10)	−0.0080 (8)	−0.0133 (8)	−0.0037 (8)
C12	0.0578 (12)	0.0464 (11)	0.0538 (12)	−0.0167 (9)	−0.0089 (9)	−0.0021 (9)
C13	0.0585 (13)	0.0740 (15)	0.0546 (12)	−0.0248 (11)	−0.0043 (10)	−0.0063 (11)
C14	0.0476 (12)	0.0792 (16)	0.0636 (14)	−0.0096 (11)	−0.0062 (10)	−0.0228 (12)
C15	0.0527 (12)	0.0503 (12)	0.0711 (14)	−0.0013 (9)	−0.0198 (11)	−0.0152 (10)
C16	0.0443 (10)	0.0391 (10)	0.0541 (11)	−0.0071 (8)	−0.0174 (9)	−0.0060 (8)
C17	0.0478 (10)	0.0353 (9)	0.0517 (11)	−0.0106 (8)	−0.0213 (9)	0.0054 (8)
C18	0.0609 (13)	0.0556 (12)	0.0571 (12)	−0.0196 (10)	−0.0153 (10)	0.0115 (10)
O5	0.1034 (15)	0.0657 (12)	0.1168 (16)	0.0254 (10)	0.0128 (12)	−0.0075 (11)
O6	0.0697 (11)	0.1044 (14)	0.0695 (11)	0.0060 (10)	0.0141 (9)	−0.0099 (10)
O7	0.0714 (10)	0.0590 (9)	0.0667 (10)	−0.0101 (8)	0.0210 (8)	−0.0078 (7)
O8	0.0604 (9)	0.0589 (9)	0.0490 (8)	−0.0115 (7)	0.0058 (6)	0.0084 (6)
N6	0.0516 (11)	0.0700 (13)	0.0706 (13)	0.0063 (9)	−0.0063 (9)	−0.0125 (10)
N7	0.0593 (10)	0.0367 (8)	0.0506 (9)	−0.0082 (7)	0.0080 (8)	0.0000 (7)
N8	0.0550 (9)	0.0439 (9)	0.0438 (9)	−0.0130 (7)	0.0013 (7)	−0.0032 (7)
N9	0.0535 (9)	0.0387 (8)	0.0454 (9)	−0.0110 (7)	0.0008 (7)	−0.0062 (7)
N10	0.0554 (10)	0.0417 (9)	0.0668 (11)	−0.0118 (8)	0.0070 (8)	−0.0069 (8)
C19	0.0433 (10)	0.0530 (11)	0.0510 (11)	−0.0007 (9)	−0.0054 (9)	−0.0089 (9)
C20	0.0653 (13)	0.0416 (11)	0.0602 (13)	0.0019 (10)	−0.0108 (11)	0.0016 (9)
C21	0.0626 (13)	0.0472 (11)	0.0490 (11)	−0.0103 (9)	−0.0011 (9)	0.0029 (9)
C22	0.0460 (10)	0.0383 (9)	0.0447 (10)	−0.0080 (8)	−0.0037 (8)	−0.0034 (8)
C23	0.0557 (12)	0.0406 (10)	0.0583 (12)	−0.0108 (9)	0.0057 (9)	0.0011 (9)
C24	0.0501 (11)	0.0577 (12)	0.0520 (11)	−0.0130 (9)	0.0040 (9)	−0.0022 (9)
C25	0.0539 (11)	0.0405 (10)	0.0447 (10)	−0.0119 (9)	−0.0011 (9)	−0.0045 (8)
C26	0.0592 (12)	0.0468 (11)	0.0448 (11)	−0.0154 (9)	0.0009 (9)	−0.0065 (9)
C27	0.0709 (14)	0.0708 (14)	0.0454 (11)	−0.0218 (12)	0.0005 (10)	0.0091 (10)
C28	0.0934 (19)	0.0759 (17)	0.0727 (16)	−0.0212 (14)	−0.0039 (14)	0.0217 (13)
C29	0.0490 (11)	0.0492 (11)	0.0506 (11)	−0.0150 (9)	−0.0033 (9)	0.0013 (9)
C30	0.0691 (14)	0.0624 (13)	0.0635 (13)	−0.0243 (11)	−0.0095 (11)	−0.0038 (11)
C31	0.0830 (18)	0.096 (2)	0.0718 (16)	−0.0378 (16)	−0.0268 (14)	0.0076 (14)
C32	0.0745 (17)	0.101 (2)	0.091 (2)	−0.0273 (16)	−0.0336 (15)	0.0261 (17)
C33	0.0617 (14)	0.0619 (14)	0.0919 (18)	−0.0097 (11)	−0.0118 (13)	0.0203 (13)
C34	0.0482 (11)	0.0489 (11)	0.0655 (13)	−0.0144 (9)	−0.0007 (10)	0.0026 (10)
C35	0.0497 (11)	0.0435 (11)	0.0515 (11)	−0.0152 (9)	0.0084 (9)	−0.0085 (8)
C36	0.0787 (15)	0.0666 (14)	0.0546 (13)	−0.0289 (12)	−0.0007 (11)	−0.0142 (10)

Geometric parameters (Å, º) top

O1—N1	1.217 (2)	O5—N6	1.226 (2)
O2—N1	1.218 (2)	O6—N6	1.220 (2)
O3—C8	1.207 (2)	O7—C26	1.200 (2)
O4—C8	1.328 (2)	O8—C26	1.331 (2)
O4—C9	1.452 (2)	O8—C27	1.455 (2)
N1—C1	1.466 (2)	N6—C19	1.471 (3)
N2—N3	1.337 (2)	N7—N8	1.342 (2)
N2—C4	1.395 (2)	N7—C22	1.392 (2)
N2—HN2	0.8600	N7—HN7	0.8600
N3—C7	1.285 (2)	N8—C25	1.288 (2)
N4—C17	1.386 (2)	N9—C35	1.383 (2)
N4—C11	1.401 (2)	N9—C29	1.403 (2)
N4—C7	1.423 (2)	N9—C25	1.422 (2)
N5—C17	1.309 (2)	N10—C35	1.309 (3)
N5—C16	1.397 (2)	N10—C34	1.397 (3)
C1—C6	1.380 (3)	C19—C20	1.378 (3)
C1—C2	1.381 (3)	C19—C24	1.382 (3)
C2—C3	1.378 (3)	C20—C21	1.377 (3)
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.391 (2)	C21—C22	1.390 (3)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.390 (3)	C22—C23	1.397 (3)
C5—C6	1.374 (3)	C23—C24	1.378 (3)
C5—H5	0.9300	C23—H23	0.9300
C6—H6	0.9300	C24—H24	0.9300
C7—C8	1.487 (3)	C25—C26	1.490 (3)
C9—C10	1.498 (3)	C27—C28	1.485 (3)
C9—H9A	0.9700	C27—H27A	0.9700
C9—H9B	0.9700	C27—H27B	0.9700
C10—H10A	0.9600	C28—H28A	0.9600
C10—H10B	0.9600	C28—H28B	0.9600
C10—H10C	0.9600	C28—H28C	0.9600
C11—C12	1.385 (3)	C29—C30	1.387 (3)
C11—C16	1.393 (2)	C29—C34	1.396 (3)
C12—C13	1.388 (3)	C30—C31	1.380 (3)
C12—H12	0.9300	C30—H30	0.9300
C13—C14	1.384 (3)	C31—C32	1.382 (4)
C13—H13	0.9300	C31—H31	0.9300
C14—C15	1.379 (3)	C32—C33	1.375 (4)
C14—H14	0.9300	C32—H32	0.9300
C15—C16	1.392 (3)	C33—C34	1.394 (3)
C15—H15	0.9300	C33—H33	0.9300
C17—C18	1.485 (3)	C35—C36	1.477 (3)
C18—H18A	0.9600	C36—H36A	0.9600
C18—H18B	0.9600	C36—H36B	0.9600
C18—H18C	0.9600	C36—H36C	0.9600

C8—O4—C9	116.83 (16)	C26—O8—C27	115.74 (16)
O1—N1—O2	122.68 (18)	O6—N6—O5	123.4 (2)
O1—N1—C1	118.63 (17)	O6—N6—C19	118.66 (19)
O2—N1—C1	118.68 (17)	O5—N6—C19	117.9 (2)
N3—N2—C4	118.31 (14)	N8—N7—C22	118.60 (15)
N3—N2—HN2	120.8	N8—N7—HN7	120.7
C4—N2—HN2	120.8	C22—N7—HN7	120.7
C7—N3—N2	119.99 (15)	C25—N8—N7	119.93 (16)
C17—N4—C11	106.86 (14)	C35—N9—C29	106.74 (15)
C17—N4—C7	129.14 (15)	C35—N9—C25	127.53 (16)
C11—N4—C7	123.94 (15)	C29—N9—C25	125.29 (15)
C17—N5—C16	105.97 (14)	C35—N10—C34	106.03 (16)
C6—C1—C2	121.48 (17)	C20—C19—C24	121.67 (18)
C6—C1—N1	119.75 (17)	C20—C19—N6	118.98 (19)
C2—C1—N1	118.76 (16)	C24—C19—N6	119.29 (19)
C3—C2—C1	119.47 (17)	C21—C20—C19	119.52 (18)
C3—C2—H2	120.3	C21—C20—H20	120.2
C1—C2—H2	120.3	C19—C20—H20	120.2
C2—C3—C4	119.62 (17)	C20—C21—C22	120.00 (19)
C2—C3—H3	120.2	C20—C21—H21	120.0
C4—C3—H3	120.2	C22—C21—H21	120.0
C5—C4—C3	120.12 (17)	C21—C22—N7	121.86 (17)
C5—C4—N2	118.87 (16)	C21—C22—C23	119.56 (17)
C3—C4—N2	120.99 (16)	N7—C22—C23	118.55 (16)
C6—C5—C4	120.21 (17)	C24—C23—C22	120.53 (18)
C6—C5—H5	119.9	C24—C23—H23	119.7
C4—C5—H5	119.9	C22—C23—H23	119.7
C5—C6—C1	119.08 (18)	C23—C24—C19	118.72 (18)
C5—C6—H6	120.5	C23—C24—H24	120.6
C1—C6—H6	120.5	C19—C24—H24	120.6
N3—C7—N4	123.59 (16)	N8—C25—N9	124.46 (17)
N3—C7—C8	118.85 (16)	N8—C25—C26	119.50 (17)
N4—C7—C8	117.48 (15)	N9—C25—C26	115.93 (16)
O3—C8—O4	125.28 (18)	O7—C26—O8	125.24 (18)
O3—C8—C7	123.09 (17)	O7—C26—C25	121.83 (19)
O4—C8—C7	111.63 (16)	O8—C26—C25	112.93 (17)
O4—C9—C10	106.55 (19)	O8—C27—C28	107.56 (18)
O4—C9—H9A	110.4	O8—C27—H27A	110.2
C10—C9—H9A	110.4	C28—C27—H27A	110.2
O4—C9—H9B	110.4	O8—C27—H27B	110.2
C10—C9—H9B	110.4	C28—C27—H27B	110.2
H9A—C9—H9B	108.6	H27A—C27—H27B	108.5
C9—C10—H10A	109.5	C27—C28—H28A	109.5
C9—C10—H10B	109.5	C27—C28—H28B	109.5
H10A—C10—H10B	109.5	H28A—C28—H28B	109.5
C9—C10—H10C	109.5	C27—C28—H28C	109.5
H10A—C10—H10C	109.5	H28A—C28—H28C	109.5
H10B—C10—H10C	109.5	H28B—C28—H28C	109.5
C12—C11—C16	122.47 (17)	C30—C29—C34	122.8 (2)
C12—C11—N4	132.62 (16)	C30—C29—N9	132.18 (18)
C16—C11—N4	104.91 (16)	C34—C29—N9	104.98 (17)
C11—C12—C13	116.67 (19)	C31—C30—C29	116.2 (2)
C11—C12—H12	121.7	C31—C30—H30	121.9
C13—C12—H12	121.7	C29—C30—H30	121.9
C14—C13—C12	121.7 (2)	C30—C31—C32	122.1 (2)
C14—C13—H13	119.2	C30—C31—H31	119.0
C12—C13—H13	119.2	C32—C31—H31	119.0
C15—C14—C13	121.2 (2)	C33—C32—C31	121.4 (2)
C15—C14—H14	119.4	C33—C32—H32	119.3
C13—C14—H14	119.4	C31—C32—H32	119.3
C14—C15—C16	118.37 (19)	C32—C33—C34	118.3 (2)
C14—C15—H15	120.8	C32—C33—H33	120.9
C16—C15—H15	120.8	C34—C33—H33	120.9
C15—C16—C11	119.65 (19)	C33—C34—C29	119.3 (2)
C15—C16—N5	130.16 (18)	C33—C34—N10	130.8 (2)
C11—C16—N5	110.17 (16)	C29—C34—N10	109.93 (18)
N5—C17—N4	112.06 (17)	N10—C35—N9	112.28 (18)
N5—C17—C18	125.37 (16)	N10—C35—C36	125.24 (18)
N4—C17—C18	122.57 (16)	N9—C35—C36	122.47 (18)
C17—C18—H18A	109.5	C35—C36—H36A	109.5
C17—C18—H18B	109.5	C35—C36—H36B	109.5
H18A—C18—H18B	109.5	H36A—C36—H36B	109.5
C17—C18—H18C	109.5	C35—C36—H36C	109.5
H18A—C18—H18C	109.5	H36A—C36—H36C	109.5
H18B—C18—H18C	109.5	H36B—C36—H36C	109.5

C4—N2—N3—C7	179.34 (16)	C22—N7—N8—C25	−176.61 (17)
O1—N1—C1—C6	−172.27 (19)	O6—N6—C19—C20	173.9 (2)
O2—N1—C1—C6	6.6 (3)	O5—N6—C19—C20	−6.2 (3)
O1—N1—C1—C2	8.6 (3)	O6—N6—C19—C24	−3.6 (3)
O2—N1—C1—C2	−172.50 (19)	O5—N6—C19—C24	176.4 (2)
C6—C1—C2—C3	0.6 (3)	C24—C19—C20—C21	0.0 (3)
N1—C1—C2—C3	179.68 (17)	N6—C19—C20—C21	−177.33 (19)
C1—C2—C3—C4	0.5 (3)	C19—C20—C21—C22	−0.2 (3)
C2—C3—C4—C5	−1.0 (3)	C20—C21—C22—N7	177.85 (19)
C2—C3—C4—N2	−179.60 (17)	C20—C21—C22—C23	−0.1 (3)
N3—N2—C4—C5	173.32 (16)	N8—N7—C22—C21	3.0 (3)
N3—N2—C4—C3	−8.1 (3)	N8—N7—C22—C23	−178.99 (17)
C3—C4—C5—C6	0.3 (3)	C21—C22—C23—C24	0.6 (3)
N2—C4—C5—C6	178.94 (18)	N7—C22—C23—C24	−177.45 (19)
C4—C5—C6—C1	0.8 (3)	C22—C23—C24—C19	−0.7 (3)
C2—C1—C6—C5	−1.3 (3)	C20—C19—C24—C23	0.4 (3)
N1—C1—C6—C5	179.64 (18)	N6—C19—C24—C23	177.78 (19)
N2—N3—C7—N4	−6.2 (3)	N7—N8—C25—N9	4.8 (3)
N2—N3—C7—C8	177.09 (15)	N7—N8—C25—C26	−179.04 (17)
C17—N4—C7—N3	116.7 (2)	C35—N9—C25—N8	−118.9 (2)
C11—N4—C7—N3	−66.5 (2)	C29—N9—C25—N8	69.7 (3)
C17—N4—C7—C8	−66.6 (2)	C35—N9—C25—C26	64.9 (2)
C11—N4—C7—C8	110.17 (19)	C29—N9—C25—C26	−106.5 (2)
C9—O4—C8—O3	1.4 (3)	C27—O8—C26—O7	−1.3 (3)
C9—O4—C8—C7	−179.17 (16)	C27—O8—C26—C25	178.91 (16)
N3—C7—C8—O3	179.47 (19)	N8—C25—C26—O7	−171.24 (19)
N4—C7—C8—O3	2.6 (3)	N9—C25—C26—O7	5.2 (3)
N3—C7—C8—O4	0.0 (2)	N8—C25—C26—O8	8.5 (3)
N4—C7—C8—O4	−176.83 (15)	N9—C25—C26—O8	−175.03 (15)
C8—O4—C9—C10	−173.35 (18)	C26—O8—C27—C28	172.01 (18)
C17—N4—C11—C12	179.24 (19)	C35—N9—C29—C30	−178.4 (2)
C7—N4—C11—C12	1.9 (3)	C25—N9—C29—C30	−5.6 (3)
C17—N4—C11—C16	−0.09 (18)	C35—N9—C29—C34	0.89 (19)
C7—N4—C11—C16	−177.45 (15)	C25—N9—C29—C34	173.76 (17)
C16—C11—C12—C13	1.2 (3)	C34—C29—C30—C31	0.5 (3)
N4—C11—C12—C13	−178.02 (18)	N9—C29—C30—C31	179.8 (2)
C11—C12—C13—C14	0.2 (3)	C29—C30—C31—C32	−1.3 (4)
C12—C13—C14—C15	−0.8 (3)	C30—C31—C32—C33	0.8 (4)
C13—C14—C15—C16	0.0 (3)	C31—C32—C33—C34	0.5 (4)
C14—C15—C16—C11	1.4 (3)	C32—C33—C34—C29	−1.2 (3)
C14—C15—C16—N5	179.41 (18)	C32—C33—C34—N10	−179.9 (2)
C12—C11—C16—C15	−2.0 (3)	C30—C29—C34—C33	0.7 (3)
N4—C11—C16—C15	177.39 (16)	N9—C29—C34—C33	−178.74 (18)
C12—C11—C16—N5	179.57 (16)	C30—C29—C34—N10	179.64 (18)
N4—C11—C16—N5	−1.01 (19)	N9—C29—C34—N10	0.2 (2)
C17—N5—C16—C15	−176.41 (19)	C35—N10—C34—C33	177.5 (2)
C17—N5—C16—C11	1.77 (19)	C35—N10—C34—C29	−1.3 (2)
C16—N5—C17—N4	−1.85 (19)	C34—N10—C35—N9	1.9 (2)
C16—N5—C17—C18	177.58 (17)	C34—N10—C35—C36	−176.71 (18)
C11—N4—C17—N5	1.26 (19)	C29—N9—C35—N10	−1.8 (2)
C7—N4—C17—N5	178.44 (16)	C25—N9—C35—N10	−174.49 (17)
C11—N4—C17—C18	−178.19 (16)	C29—N9—C35—C36	176.86 (17)
C7—N4—C17—C18	−1.0 (3)	C25—N9—C35—C36	4.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···N5ⁱ	0.86	2.19	2.954 (2)	148
N7—HN7···N10ⁱⁱ	0.86	2.19	2.967 (2)	150

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇N₅O₄
M_r	367.37
Crystal system, space group	Triclinic, P1
Temperature (K)	300
a, b, c (Å)	8.269 (3), 11.523 (2), 19.853 (6)
α, β, γ (°)	87.44 (2), 80.67 (3), 76.80 (2)
V (Å³)	1817.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.4 × 0.18 × 0.12

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9121, 7912, 4441
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.131, 1.01
No. of reflections	7912
No. of parameters	492
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), MolEN (Fair, 1990), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···N5ⁱ	0.860	2.193	2.954 (2)	147.49
N7—HN7···N10ⁱⁱ	0.860	2.190	2.967 (2)	150.16

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

Références

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Volume 67| Part 7| juillet 2011| Page o1569

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