5-(4-Meth­oxy­phen­yl)-4-methyl-1-phenyl-3-p-tolyl-1H-pyrazole

Ben Soumane, Y.; Loughzail, M.; Baouid, A.; El Hadrami, E.M.; Ben Tama, A.; Driss, M.

doi:10.1107/S2414314617016261

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171626

https://doi.org/10.1107/S2414314617016261

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5-(4-Methoxyphenyl)-4-methyl-1-phenyl-3-p-tolyl-1H-pyrazole

Yahya Ben Soumane,^a Mohamed Loughzail,^b ^* Abdesselam Baouid,^b El Mestafa El Hadrami,^a Abdeslam Ben Tama ^a and Mohamed Driss ^c

^aLaboratoire de Chimie Organique Appliquée, Departement de Chimie, Faculté des Sciences et Techniques, BP 2202, Université Sidi Mohamed Ben Abdellah, Fès, Morocco, ^bLaboratoire de Chimie Moléculaire, Département de Chimie, Faculté, des Sciences Semlalia, BP 2390, Université Cadi Ayyad, 40001, Marrakech, Morocco, and ^cLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis ElManar, 2092 ElManar II, Tunis, Tunisia
^*Correspondence e-mail: loughzail@gmail.com

Edited by H. Ishida, Okayama University, Japan (Received 31 October 2017; accepted 10 November 2017; online 17 November 2017)

The title compound, C₂₄H₂₂N₂O, crystallizes with two independent molecules (A and B) in the asymmetric unit. The phenyl, p-tolyl and p-methoxyphenyl rings are inclined to the pyrazole ring by 42.5 (2), 17.68 (19) and 52.20 (19)°, respectively, in molecule A, and by 39.5 (2), 40.77 (19) and 59.76 (18)°, respectively, in molecule B. In the asymmetric unit, the pyrarole ring of molecule A makes a dihedral angle of 3.7 (2)° with that of molecule B. In the crystal, the two independent molecules are linked to each other by a C—H⋯O hydrogen bond.

Keywords: crystal structure; pyrazole; trans-anethole,diaryl nitrilimine; 1,3-dipolar cycloaddition.

CCDC reference: 1584986

Structure description

Trans-anethole {systematic name: 1-methoxy-4-[(E)-prop-1-en-1-yl]benzene} is an active ingredient of the essential oil of anise and the source of the aniseed scent. It has antigenotoxic (Abraham et al., 2001 ), gastroprotective and antioxidative (Freire et al., 2005 ), and antimicrobial and antiviral (Astani et al., 2010 ) properties. The molecule has a double bond in the aromatic portion, which confers some reactivity. In this work, we focused our efforts on the preparation of new pentagonal heterocyclic systems by the 1,3-dipolar cycloaddition reaction from trans-anethole and diarylnitrilimine.

The molecular structure of the title compound is illustrated in Fig. 1. The main geometric features are in good agreement with those observed in a similar compound (Loughzail et al., 2014 ). In the crystal, the two crystallographically independent molecules are linked to each other into a dimer via a C—H⋯O hydrogen bond (C50—H50⋯O1ⁱ; Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C50—H50⋯O1ⁱ	0.93	2.44	3.327 (4)	160
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Figure 1
The asymmetric unit of the title compound with the atom-labelling scheme and 30% probability ellipsoids for non-H atoms.

Figure 2
A partial packing diagram of the title compound viewed down the a axis, showing the C—H⋯O hydrogen bonds as blue lines.

Synthesis and crystallization

Triethylamine (9 mmol) dissolved in dichloromethane (5 ml) was added dropwise to a solution of anethole (6.74 mmol) and the precursor diarylnitrilimine (6.74 mmol) (Huisgen et al., 1962 ) in dichloromethane (20 ml). After stirring for one day at room temperature, the mixture was washed several times with water (25 ml). The organic layers were separated, dried by anhydrous sodium sulfate, filtered and evaporated. The residue was purified in a silica gel column (eluent: hexane–ethyl acetate 2:98 v/v). We have isolated two products 1 and 2. Only the compound 2 is treated in this work. Single crystals of the title compound were obtained from a mixed solution of hexane and ethyl acetate (2:98 v/v) at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₂₂N₂O
M_r	354.43
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	11.615 (5), 17.562 (4), 18.847 (8)
V (Å³)	3844 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.25 × 0.22

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.441, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	9494, 7577, 4885
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.117, 1.00
No. of reflections	7577
No. of parameters	494
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1584986

Crystal structure: contains datablocks I, block. DOI: https://doi.org/10.1107/S2414314617016261/is4019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617016261/is4019Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

5-(4-Methoxyphenyl)-4-methyl-1-phenyl-3-p-tolyl-1H-pyrazole top

Crystal data top

C₂₄H₂₂N₂O	D_x = 1.225 Mg m⁻³
M_r = 354.43	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7577 reflections
a = 11.615 (5) Å	θ = 2.1–26.4°
b = 17.562 (4) Å	µ = 0.08 mm⁻¹
c = 18.847 (8) Å	T = 293 K
V = 3844 (2) Å³	Box, white
Z = 8	0.30 × 0.25 × 0.22 mm
F(000) = 1504

Data collection top

Bruker X8 APEX diffractometer	4885 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.029
φ and ω scans	θ_max = 26.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→14
T_min = 0.441, T_max = 0.981	k = −21→16
9494 measured reflections	l = −8→23
7577 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0611P)² + 0.0246P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.16 e Å⁻³
7577 reflections	Δρ_min = −0.17 e Å⁻³
494 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0037 (7)

Special details top

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

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

	x	y	z	U_iso*/U_eq
O1	0.3907 (2)	0.61275 (12)	0.07832 (13)	0.0600 (7)
O2	0.6071 (2)	0.44506 (13)	0.18934 (14)	0.0618 (7)
N1	0.1252 (2)	0.20939 (14)	0.10883 (13)	0.0459 (7)
N2	0.1370 (2)	0.28613 (14)	0.10968 (14)	0.0450 (7)
N3	0.8590 (2)	0.85027 (14)	0.12709 (13)	0.0436 (6)
N4	0.8512 (2)	0.77294 (13)	0.12969 (13)	0.0414 (6)
C1	0.3896 (4)	0.6563 (2)	0.1417 (2)	0.0702 (11)
H1A	0.417712	0.706600	0.131989	0.105*
H1B	0.437952	0.632338	0.176426	0.105*
H1C	0.312272	0.659319	0.159469	0.105*
C2	0.3526 (3)	0.53972 (17)	0.08170 (17)	0.0445 (8)
C3	0.3190 (3)	0.50307 (18)	0.14364 (16)	0.0451 (8)
H3	0.322648	0.528430	0.186900	0.054*
C4	0.2804 (3)	0.42947 (18)	0.14076 (16)	0.0443 (8)
H4	0.257938	0.405475	0.182511	0.053*
C5	0.2740 (3)	0.38955 (18)	0.07710 (16)	0.0437 (7)
C6	0.3081 (3)	0.42728 (19)	0.01563 (17)	0.0525 (9)
H6	0.304020	0.402153	−0.027736	0.063*
C7	0.3475 (3)	0.50075 (19)	0.01787 (17)	0.0535 (9)
H7	0.370943	0.524624	−0.023734	0.064*
C8	0.2350 (3)	0.30971 (18)	0.07626 (16)	0.0461 (8)
C9	0.2886 (3)	0.2449 (2)	0.05149 (17)	0.0487 (8)
C10	0.4015 (4)	0.2431 (2)	0.0128 (2)	0.0820 (14)
H10A	0.394819	0.210908	−0.028235	0.123*
H10B	0.460165	0.223427	0.043604	0.123*
H10C	0.421641	0.293692	−0.001873	0.123*
C11	0.2172 (3)	0.18364 (18)	0.07349 (16)	0.0440 (8)
C12	0.2317 (3)	0.10019 (18)	0.06841 (15)	0.0438 (8)
C13	0.3356 (3)	0.0659 (2)	0.05164 (19)	0.0574 (9)
H13	0.397459	0.095733	0.037359	0.069*
C14	0.1405 (3)	0.05216 (19)	0.08543 (19)	0.0549 (9)
H14	0.068522	0.073049	0.094795	0.066*
C15	0.3483 (3)	−0.0120 (2)	0.05586 (19)	0.0580 (9)
H15	0.419332	−0.033240	0.044624	0.070*
C16	0.1545 (3)	−0.0256 (2)	0.08871 (18)	0.0566 (9)
H16	0.091462	−0.055996	0.099709	0.068*
C17	0.2599 (3)	−0.05963 (19)	0.07607 (17)	0.0516 (9)
C18	0.2776 (4)	−0.1432 (2)	0.0865 (2)	0.0686 (11)
H18A	0.207149	−0.169697	0.076515	0.103*
H18B	0.300122	−0.152720	0.134700	0.103*
H18C	0.336832	−0.160790	0.055011	0.103*
C19	0.0522 (3)	0.32924 (18)	0.14675 (17)	0.0449 (8)
C20	0.0128 (3)	0.3022 (2)	0.21083 (17)	0.0551 (9)
H20	0.040889	0.256601	0.228984	0.066*
C21	0.0098 (3)	0.39652 (18)	0.11932 (19)	0.0551 (9)
H21	0.035792	0.414732	0.075852	0.066*
C22	−0.0685 (3)	0.3431 (2)	0.2479 (2)	0.0675 (11)
H22	−0.094828	0.325044	0.291347	0.081*
C23	−0.0719 (3)	0.4363 (2)	0.1575 (2)	0.0664 (11)
H23	−0.100984	0.481672	0.139356	0.080*
C24	−0.1109 (3)	0.4100 (2)	0.2216 (2)	0.0713 (12)
H24	−0.165644	0.437435	0.247008	0.086*
C31	0.5970 (4)	0.39782 (19)	0.1281 (2)	0.0701 (11)
H31A	0.569242	0.348494	0.141874	0.105*
H31B	0.670928	0.392678	0.105867	0.105*
H31C	0.543837	0.420494	0.095265	0.105*
C32	0.6434 (3)	0.51809 (18)	0.17963 (17)	0.0466 (8)
C33	0.6633 (3)	0.55078 (17)	0.11367 (17)	0.0473 (8)
H33	0.652377	0.522615	0.072428	0.057*
C34	0.6995 (3)	0.62521 (17)	0.10999 (16)	0.0464 (8)
H34	0.711752	0.646939	0.065629	0.056*
C35	0.7185 (3)	0.66915 (17)	0.17020 (15)	0.0399 (7)
C36	0.6979 (3)	0.63489 (19)	0.23567 (16)	0.0501 (8)
H36	0.709410	0.662726	0.277048	0.060*
C37	0.6610 (3)	0.5608 (2)	0.24019 (18)	0.0534 (9)
H37	0.647678	0.539093	0.284466	0.064*
C38	0.7539 (3)	0.74977 (18)	0.16443 (15)	0.0416 (7)
C39	0.6965 (3)	0.81413 (19)	0.18527 (16)	0.0452 (8)
C40	0.5837 (3)	0.8173 (2)	0.2233 (2)	0.0630 (10)
H40A	0.581630	0.861504	0.253183	0.095*
H40B	0.574666	0.772371	0.251761	0.095*
H40C	0.522278	0.820008	0.189263	0.095*
C41	0.7656 (3)	0.87515 (17)	0.16080 (15)	0.0407 (7)
C42	0.7479 (3)	0.95839 (17)	0.16699 (15)	0.0429 (8)
C43	0.6422 (3)	0.9920 (2)	0.1569 (2)	0.0575 (9)
H43	0.578354	0.961348	0.148218	0.069*
C44	0.8406 (3)	1.00620 (19)	0.18066 (17)	0.0496 (8)
H44	0.913078	0.985398	0.188486	0.060*
C45	0.6285 (3)	1.0697 (2)	0.15938 (19)	0.0622 (10)
H45	0.555578	1.090348	0.152831	0.075*
C46	0.8263 (3)	1.0847 (2)	0.18279 (19)	0.0571 (10)
H46	0.889482	1.115594	0.192148	0.069*
C47	0.7200 (4)	1.1177 (2)	0.17129 (19)	0.0589 (10)
C48	0.7046 (5)	1.2031 (2)	0.1710 (3)	0.0912 (15)
H48A	0.743677	1.224671	0.211073	0.137*
H48B	0.624030	1.215025	0.173644	0.137*
H48C	0.736124	1.223728	0.128029	0.137*
C49	0.9395 (3)	0.72868 (17)	0.09685 (17)	0.0418 (8)
C50	0.9843 (3)	0.75376 (19)	0.03285 (17)	0.0503 (8)
H50	0.957752	0.798646	0.012419	0.060*
C51	0.9805 (3)	0.66320 (19)	0.12800 (19)	0.0548 (9)
H51	0.952290	0.647393	0.171771	0.066*
C52	1.0688 (3)	0.7114 (2)	−0.0003 (2)	0.0598 (10)
H52	1.099358	0.727963	−0.043213	0.072*
C53	1.0642 (3)	0.6211 (2)	0.0934 (2)	0.0643 (10)
H53	1.090963	0.576157	0.113607	0.077*
C54	1.1081 (3)	0.6450 (2)	0.0298 (2)	0.0649 (11)
H54	1.164328	0.616321	0.006960	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0741 (16)	0.0462 (14)	0.0597 (14)	−0.0098 (13)	−0.0039 (14)	0.0067 (11)
O2	0.0678 (16)	0.0454 (14)	0.0721 (16)	−0.0050 (13)	0.0089 (14)	0.0112 (12)
N1	0.0503 (16)	0.0393 (16)	0.0480 (15)	0.0027 (13)	−0.0005 (14)	−0.0044 (12)
N2	0.0473 (17)	0.0444 (16)	0.0434 (15)	0.0020 (13)	0.0024 (13)	−0.0037 (12)
N3	0.0492 (16)	0.0400 (15)	0.0415 (14)	0.0016 (13)	0.0025 (13)	0.0003 (11)
N4	0.0463 (16)	0.0366 (15)	0.0412 (14)	0.0029 (12)	0.0019 (13)	0.0002 (11)
C1	0.086 (3)	0.046 (2)	0.078 (3)	−0.007 (2)	−0.008 (2)	−0.0056 (19)
C2	0.0439 (18)	0.0408 (19)	0.0489 (18)	0.0001 (15)	−0.0064 (16)	0.0034 (15)
C3	0.0548 (19)	0.0447 (19)	0.0358 (16)	−0.0002 (16)	−0.0025 (15)	−0.0022 (14)
C4	0.0505 (19)	0.0479 (19)	0.0346 (15)	−0.0001 (16)	0.0016 (15)	0.0025 (14)
C5	0.0467 (18)	0.0467 (18)	0.0378 (16)	−0.0006 (16)	−0.0011 (16)	0.0010 (14)
C6	0.065 (2)	0.056 (2)	0.0366 (17)	−0.0001 (19)	0.0025 (16)	−0.0025 (15)
C7	0.066 (2)	0.053 (2)	0.0418 (18)	−0.002 (2)	0.0053 (18)	0.0086 (15)
C8	0.056 (2)	0.0486 (19)	0.0340 (15)	−0.0028 (17)	0.0000 (16)	−0.0028 (14)
C9	0.055 (2)	0.048 (2)	0.0431 (17)	0.0005 (18)	0.0046 (17)	−0.0057 (15)
C10	0.086 (3)	0.062 (3)	0.098 (3)	−0.006 (2)	0.048 (3)	−0.012 (2)
C11	0.0502 (19)	0.0447 (18)	0.0372 (16)	0.0029 (17)	−0.0023 (16)	−0.0043 (14)
C12	0.0494 (19)	0.0464 (19)	0.0355 (16)	0.0019 (17)	0.0002 (16)	−0.0042 (13)
C13	0.054 (2)	0.056 (2)	0.062 (2)	−0.0011 (19)	0.0084 (19)	−0.0053 (18)
C14	0.049 (2)	0.053 (2)	0.062 (2)	0.0038 (17)	0.0077 (19)	−0.0031 (17)
C15	0.054 (2)	0.058 (2)	0.061 (2)	0.015 (2)	0.0041 (19)	−0.0093 (18)
C16	0.059 (2)	0.049 (2)	0.061 (2)	−0.0015 (18)	0.0105 (19)	−0.0041 (18)
C17	0.063 (2)	0.049 (2)	0.0431 (18)	0.004 (2)	−0.0049 (18)	−0.0082 (15)
C18	0.082 (3)	0.055 (2)	0.068 (2)	0.013 (2)	0.005 (2)	−0.004 (2)
C19	0.0393 (17)	0.047 (2)	0.0485 (19)	0.0030 (15)	−0.0057 (15)	−0.0079 (15)
C20	0.0467 (19)	0.066 (2)	0.052 (2)	0.0113 (19)	0.0012 (18)	−0.0035 (18)
C21	0.055 (2)	0.052 (2)	0.059 (2)	0.0073 (18)	−0.0079 (19)	−0.0030 (17)
C22	0.057 (2)	0.089 (3)	0.057 (2)	0.010 (2)	0.005 (2)	−0.010 (2)
C23	0.054 (2)	0.054 (2)	0.091 (3)	0.0135 (19)	−0.013 (2)	−0.009 (2)
C24	0.045 (2)	0.085 (3)	0.083 (3)	0.015 (2)	0.000 (2)	−0.024 (2)
C31	0.071 (3)	0.042 (2)	0.098 (3)	−0.0032 (19)	0.010 (2)	−0.002 (2)
C32	0.0457 (19)	0.0405 (19)	0.0535 (19)	0.0045 (16)	0.0050 (17)	0.0078 (16)
C33	0.054 (2)	0.0426 (19)	0.0457 (18)	−0.0001 (16)	0.0017 (16)	0.0001 (14)
C34	0.056 (2)	0.047 (2)	0.0360 (17)	−0.0026 (16)	0.0025 (15)	0.0023 (14)
C35	0.0389 (17)	0.0427 (19)	0.0379 (16)	−0.0009 (15)	0.0009 (14)	0.0014 (13)
C36	0.061 (2)	0.052 (2)	0.0368 (17)	0.0026 (18)	0.0015 (16)	0.0007 (15)
C37	0.060 (2)	0.058 (2)	0.0428 (17)	0.0002 (19)	0.0076 (17)	0.0102 (16)
C38	0.0443 (18)	0.0461 (18)	0.0345 (16)	−0.0003 (17)	−0.0035 (14)	−0.0010 (14)
C39	0.0431 (18)	0.053 (2)	0.0391 (16)	−0.0016 (17)	−0.0024 (15)	−0.0105 (15)
C40	0.052 (2)	0.065 (2)	0.072 (2)	−0.006 (2)	0.012 (2)	−0.021 (2)
C41	0.0440 (18)	0.0439 (19)	0.0342 (15)	0.0019 (16)	−0.0043 (15)	−0.0039 (13)
C42	0.0502 (19)	0.0434 (19)	0.0352 (16)	0.0036 (16)	0.0014 (15)	−0.0048 (13)
C43	0.051 (2)	0.055 (2)	0.066 (2)	0.0045 (19)	−0.0041 (19)	−0.0040 (17)
C44	0.051 (2)	0.048 (2)	0.0499 (19)	0.0069 (17)	0.0033 (17)	−0.0034 (15)
C45	0.059 (2)	0.058 (2)	0.070 (2)	0.015 (2)	0.002 (2)	0.0017 (19)
C46	0.067 (2)	0.048 (2)	0.057 (2)	−0.0054 (19)	0.002 (2)	−0.0076 (17)
C47	0.076 (3)	0.043 (2)	0.057 (2)	0.009 (2)	0.011 (2)	−0.0014 (16)
C48	0.118 (4)	0.047 (2)	0.109 (4)	0.013 (3)	0.017 (3)	−0.001 (2)
C49	0.0397 (17)	0.0391 (18)	0.0465 (18)	−0.0001 (14)	−0.0010 (15)	−0.0040 (14)
C50	0.055 (2)	0.0459 (19)	0.0504 (19)	0.0017 (18)	0.0050 (18)	−0.0004 (16)
C51	0.053 (2)	0.050 (2)	0.062 (2)	0.0086 (18)	0.0002 (19)	0.0055 (17)
C52	0.051 (2)	0.068 (3)	0.060 (2)	−0.001 (2)	0.0128 (19)	−0.0093 (19)
C53	0.054 (2)	0.050 (2)	0.089 (3)	0.0123 (19)	−0.001 (2)	0.003 (2)
C54	0.048 (2)	0.062 (2)	0.085 (3)	0.009 (2)	0.010 (2)	−0.014 (2)

Geometric parameters (Å, º) top

O1—C1	1.418 (4)	C22—H22	0.9300
O1—C2	1.358 (4)	C23—C24	1.371 (5)
O2—C31	1.427 (4)	C23—H23	0.9300
O2—C32	1.362 (4)	C24—H24	0.9300
N1—C11	1.337 (4)	C31—H31A	0.9600
N2—N1	1.355 (3)	C31—H31B	0.9600
N2—C8	1.365 (4)	C31—H31C	0.9600
N4—N3	1.362 (3)	C32—C37	1.381 (5)
N4—C38	1.367 (4)	C32—C33	1.389 (4)
C1—H1A	0.9600	C33—H33	0.9300
C1—H1B	0.9600	C34—C33	1.375 (4)
C1—H1C	0.9600	C34—C35	1.390 (4)
C3—C4	1.369 (4)	C34—H34	0.9300
C3—C2	1.389 (4)	C35—C38	1.478 (4)
C3—H3	0.9300	C36—C37	1.374 (5)
C4—C5	1.392 (4)	C36—C35	1.393 (4)
C4—H4	0.9300	C36—H36	0.9300
C5—C6	1.392 (4)	C37—H37	0.9300
C6—H6	0.9300	C38—C39	1.370 (4)
C7—C2	1.385 (4)	C39—C40	1.494 (5)
C7—C6	1.370 (4)	C40—H40A	0.9600
C7—H7	0.9300	C40—H40B	0.9600
C8—C5	1.473 (4)	C40—H40C	0.9600
C8—C9	1.379 (4)	C41—N3	1.331 (4)
C9—C10	1.501 (5)	C41—C39	1.416 (4)
C10—H10A	0.9600	C42—C43	1.376 (5)
C10—H10B	0.9600	C42—C44	1.389 (5)
C10—H10C	0.9600	C42—C41	1.481 (4)
C11—C9	1.420 (5)	C43—C45	1.375 (5)
C12—C13	1.385 (5)	C43—H43	0.9300
C12—C14	1.391 (5)	C44—C46	1.389 (5)
C12—C11	1.478 (4)	C44—H44	0.9300
C13—C15	1.377 (5)	C45—C47	1.375 (5)
C13—H13	0.9300	C45—H45	0.9300
C14—C16	1.376 (5)	C46—C47	1.380 (5)
C14—H14	0.9300	C46—H46	0.9300
C15—C17	1.378 (5)	C47—C48	1.510 (5)
C15—H15	0.9300	C48—H48A	0.9600
C16—C17	1.383 (5)	C48—H48B	0.9600
C16—H16	0.9300	C48—H48C	0.9600
C17—C18	1.495 (5)	C49—C51	1.376 (4)
C18—H18A	0.9600	C49—C50	1.386 (4)
C18—H18B	0.9600	C49—N4	1.428 (4)
C18—H18C	0.9600	C50—C52	1.380 (5)
C19—C20	1.376 (4)	C50—H50	0.9300
C19—C21	1.381 (4)	C51—C53	1.385 (5)
C19—N2	1.426 (4)	C51—H51	0.9300
C20—C22	1.377 (5)	C52—C54	1.376 (5)
C20—H20	0.9300	C52—H52	0.9300
C21—C23	1.380 (5)	C53—C54	1.368 (5)
C21—H21	0.9300	C53—H53	0.9300
C22—C24	1.367 (5)	C54—H54	0.9300

C2—O1—C1	117.8 (3)	C24—C23—H23	119.5
C41—N3—N4	104.8 (3)	C21—C23—H23	119.5
C32—O2—C31	117.7 (3)	C22—C24—C23	119.3 (4)
C11—N1—N2	105.2 (3)	C22—C24—H24	120.3
N1—N2—C8	112.4 (3)	C23—C24—H24	120.3
N1—N2—C19	117.6 (3)	O2—C31—H31A	109.5
N3—N4—C38	111.7 (2)	O2—C31—H31B	109.5
N3—N4—C49	118.6 (3)	H31A—C31—H31B	109.5
C38—N4—C49	129.7 (2)	O2—C31—H31C	109.5
C8—N2—C19	129.9 (3)	H31A—C31—H31C	109.5
O1—C1—H1A	109.5	H31B—C31—H31C	109.5
O1—C1—H1B	109.5	O2—C32—C37	116.5 (3)
O1—C1—H1C	109.5	O2—C32—C33	124.1 (3)
H1A—C1—H1B	109.5	C37—C32—C33	119.4 (3)
H1A—C1—H1C	109.5	C34—C33—C32	119.3 (3)
H1B—C1—H1C	109.5	C34—C33—H33	120.4
O1—C2—C7	116.1 (3)	C32—C33—H33	120.4
O1—C2—C3	124.7 (3)	C33—C34—C35	122.4 (3)
C7—C2—C3	119.2 (3)	C33—C34—H34	118.8
C4—C3—C2	119.7 (3)	C35—C34—H34	118.8
C4—C3—H3	120.1	C34—C35—C36	117.1 (3)
C2—C3—H3	120.1	C34—C35—C38	121.0 (3)
C3—C4—C5	121.8 (3)	C36—C35—C38	121.8 (3)
C3—C4—H4	119.1	C37—C36—C35	121.2 (3)
C5—C4—H4	119.1	C37—C36—H36	119.4
C4—C5—C6	117.5 (3)	C35—C36—H36	119.4
C4—C5—C8	120.3 (3)	C36—C37—C32	120.6 (3)
C6—C5—C8	122.1 (3)	C36—C37—H37	119.7
C7—C6—C5	121.2 (3)	C32—C37—H37	119.7
C7—C6—H6	119.4	N4—C38—C39	107.1 (3)
C5—C6—H6	119.4	N4—C38—C35	123.4 (3)
C6—C7—C2	120.4 (3)	C39—C38—C35	129.3 (3)
C6—C7—H7	119.8	C38—C39—C41	104.8 (3)
C2—C7—H7	119.8	C38—C39—C40	126.5 (3)
N2—C8—C9	106.4 (3)	C41—C39—C40	128.7 (3)
N2—C8—C5	122.7 (3)	C39—C40—H40A	109.5
C9—C8—C5	130.6 (3)	C39—C40—H40B	109.5
C8—C9—C11	105.3 (3)	H40A—C40—H40B	109.5
C8—C9—C10	125.2 (3)	C39—C40—H40C	109.5
C11—C9—C10	129.5 (3)	H40A—C40—H40C	109.5
C9—C10—H10A	109.5	H40B—C40—H40C	109.5
C9—C10—H10B	109.5	N3—C41—C39	111.7 (3)
H10A—C10—H10B	109.5	N3—C41—C42	118.3 (3)
C9—C10—H10C	109.5	C39—C41—C42	130.0 (3)
H10A—C10—H10C	109.5	C43—C42—C44	117.3 (3)
H10B—C10—H10C	109.5	C43—C42—C41	122.4 (3)
N1—C11—C9	110.8 (3)	C44—C42—C41	120.3 (3)
N1—C11—C12	117.3 (3)	C45—C43—C42	121.6 (3)
C9—C11—C12	131.7 (3)	C45—C43—H43	119.2
C13—C12—C14	116.8 (3)	C42—C43—H43	119.2
C13—C12—C11	123.1 (3)	C42—C44—C46	120.9 (3)
C14—C12—C11	119.9 (3)	C42—C44—H44	119.6
C15—C13—C12	120.8 (4)	C46—C44—H44	119.6
C15—C13—H13	119.6	C47—C45—C43	121.7 (4)
C12—C13—H13	119.6	C47—C45—H45	119.2
C16—C14—C12	121.5 (3)	C43—C45—H45	119.2
C16—C14—H14	119.3	C47—C46—C44	121.3 (4)
C12—C14—H14	119.3	C47—C46—H46	119.4
C13—C15—C17	122.6 (3)	C44—C46—H46	119.4
C13—C15—H15	118.7	C45—C47—C46	117.4 (3)
C17—C15—H15	118.7	C45—C47—C48	121.1 (4)
C14—C16—C17	121.7 (4)	C46—C47—C48	121.6 (4)
C14—C16—H16	119.1	C47—C48—H48A	109.5
C17—C16—H16	119.1	C47—C48—H48B	109.5
C15—C17—C16	116.4 (3)	H48A—C48—H48B	109.5
C15—C17—C18	122.0 (3)	C47—C48—H48C	109.5
C16—C17—C18	121.6 (4)	H48A—C48—H48C	109.5
C17—C18—H18A	109.5	H48B—C48—H48C	109.5
C17—C18—H18B	109.5	C51—C49—C50	120.5 (3)
H18A—C18—H18B	109.5	C51—C49—N4	121.2 (3)
C17—C18—H18C	109.5	C50—C49—N4	118.3 (3)
H18A—C18—H18C	109.5	C52—C50—C49	119.3 (3)
H18B—C18—H18C	109.5	C52—C50—H50	120.3
C20—C19—C21	120.4 (3)	C49—C50—H50	120.3
C20—C19—N2	118.5 (3)	C49—C51—C53	119.2 (3)
C21—C19—N2	121.2 (3)	C49—C51—H51	120.4
C19—C20—C22	119.5 (3)	C53—C51—H51	120.4
C19—C20—H20	120.2	C54—C52—C50	120.4 (4)
C22—C20—H20	120.2	C54—C52—H52	119.8
C23—C21—C19	118.9 (4)	C50—C52—H52	119.8
C23—C21—H21	120.5	C54—C53—C51	120.7 (4)
C19—C21—H21	120.5	C54—C53—H53	119.6
C24—C22—C20	120.8 (4)	C51—C53—H53	119.6
C24—C22—H22	119.6	C53—C54—C52	119.8 (4)
C20—C22—H22	119.6	C53—C54—H54	120.1
C24—C23—C21	121.0 (4)	C52—C54—H54	120.1

C1—O1—C2—C3	−4.0 (5)	C20—C22—C24—C23	0.1 (5)
C1—O1—C2—C7	175.7 (3)	C21—C23—C24—C22	−0.3 (5)
C11—N1—N2—C8	−0.6 (3)	C41—N3—N4—C38	0.2 (3)
C11—N1—N2—C19	−177.7 (3)	C41—N3—N4—C49	179.3 (3)
N2—N1—C11—C9	0.0 (3)	N4—N3—C41—C39	−0.2 (3)
N2—N1—C11—C12	175.9 (3)	N4—N3—C41—C42	−179.7 (3)
N1—N2—C8—C5	−172.8 (3)	N3—N4—C38—C35	174.9 (3)
N1—N2—C8—C9	1.0 (3)	N3—N4—C38—C39	−0.1 (3)
C19—N2—C8—C5	3.8 (5)	C49—N4—C38—C35	−4.1 (5)
C19—N2—C8—C9	177.6 (3)	C49—N4—C38—C39	−179.1 (3)
N1—N2—C19—C20	41.0 (4)	N3—N4—C49—C50	−39.0 (4)
N1—N2—C19—C21	−138.9 (3)	N3—N4—C49—C51	140.3 (3)
C8—N2—C19—C20	−135.5 (3)	C38—N4—C49—C50	140.0 (3)
C8—N2—C19—C21	44.7 (5)	C38—N4—C49—C51	−40.8 (5)
O1—C2—C3—C4	179.1 (3)	O2—C32—C33—C34	179.8 (3)
C7—C2—C3—C4	−0.6 (5)	C37—C32—C33—C34	−0.4 (5)
O1—C2—C7—C6	−178.7 (3)	O2—C32—C37—C36	179.8 (3)
C3—C2—C7—C6	1.0 (5)	C33—C32—C37—C36	−0.1 (5)
C31—O2—C32—C37	−175.1 (3)	C32—C33—C34—C35	0.8 (5)
C31—O2—C32—C33	4.7 (5)	C33—C34—C35—C36	−0.8 (5)
C2—C3—C4—C5	0.2 (5)	C33—C34—C35—C38	−178.1 (3)
C3—C4—C5—C6	−0.2 (5)	C34—C35—C36—C37	0.3 (5)
C3—C4—C5—C8	178.3 (3)	C38—C35—C36—C37	177.6 (3)
C8—C5—C6—C7	−177.9 (3)	C34—C35—C38—N4	−58.1 (5)
C4—C5—C8—N2	49.4 (5)	C34—C35—C38—C39	115.8 (4)
C6—C5—C8—N2	−132.2 (3)	C36—C35—C38—N4	124.7 (3)
C6—C5—C8—C9	55.7 (5)	C36—C35—C38—C39	−61.4 (5)
C4—C5—C8—C9	−122.8 (4)	C35—C36—C37—C32	0.1 (5)
C4—C5—C6—C7	0.6 (5)	N4—C38—C39—C40	178.2 (3)
C5—C6—C7—C2	−1.0 (5)	N4—C38—C39—C41	0.0 (3)
C5—C8—C9—C10	−5.2 (6)	C35—C38—C39—C40	3.5 (5)
C5—C8—C9—C11	172.2 (3)	C35—C38—C39—C41	−174.7 (3)
N2—C8—C9—C11	−0.9 (3)	C38—C39—C41—N3	0.1 (4)
N2—C8—C9—C10	−178.3 (3)	C38—C39—C41—C42	179.6 (3)
C8—C9—C11—N1	0.6 (4)	C40—C39—C41—N3	−178.0 (3)
C10—C9—C11—C12	2.7 (6)	C40—C39—C41—C42	1.5 (6)
C8—C9—C11—C12	−174.5 (3)	N3—C41—C42—C43	137.5 (3)
C10—C9—C11—N1	177.9 (3)	N3—C41—C42—C44	−39.8 (4)
C9—C11—C12—C13	13.4 (5)	C39—C41—C42—C43	−41.9 (5)
C9—C11—C12—C14	−171.0 (3)	C39—C41—C42—C44	140.7 (3)
N1—C11—C12—C13	−161.5 (3)	C41—C42—C43—C45	−176.7 (3)
N1—C11—C12—C14	14.2 (4)	C44—C42—C43—C45	0.7 (5)
C11—C12—C14—C16	−172.9 (3)	C41—C42—C44—C46	176.5 (3)
C11—C12—C13—C15	172.2 (3)	C43—C42—C44—C46	−1.0 (5)
C14—C12—C13—C15	−3.6 (5)	C42—C43—C45—C47	0.7 (6)
C13—C12—C14—C16	3.0 (5)	C42—C44—C46—C47	−0.1 (5)
C12—C13—C15—C17	0.5 (5)	C43—C45—C47—C46	−1.8 (5)
C12—C14—C16—C17	0.7 (5)	C43—C45—C47—C48	177.6 (4)
C13—C15—C17—C18	−174.6 (3)	C44—C46—C47—C45	1.5 (5)
C13—C15—C17—C16	3.2 (5)	C44—C46—C47—C48	−177.8 (4)
C14—C16—C17—C15	−3.8 (5)	N4—C49—C50—C52	−179.2 (3)
C14—C16—C17—C18	174.0 (3)	C51—C49—C50—C52	1.5 (5)
N2—C19—C20—C22	179.5 (3)	N4—C49—C51—C53	178.4 (3)
C20—C19—C21—C23	0.5 (5)	C50—C49—C51—C53	−2.3 (5)
C21—C19—C20—C22	−0.7 (5)	C49—C50—C52—C54	0.0 (5)
N2—C19—C21—C23	−179.7 (3)	C49—C51—C53—C54	1.6 (5)
C19—C20—C22—C24	0.3 (5)	C50—C52—C54—C53	−0.7 (5)
C19—C21—C23—C24	0.0 (5)	C51—C53—C54—C52	−0.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C50—H50···O1ⁱ	0.93	2.44	3.327 (4)	160

Symmetry code: (i) x+1/2, −y+3/2, −z.

Acknowledgements

The authors express their thanks to Professor M. Berraho and Professor E. Soumhi for their valuable contribution in order to finalize this paper.

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