4-(4-Bromo­phen­yl)-2-(3-(4-chloro­phen­yl)-5-{3-[5-methyl-1-(4-methyl­phen­yl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-di­hydro-1H-pyrazol-1-yl)thia­zole

El-Hiti, G.A.; Mohamed, H.A.; Abdel-Wahab, B.F.; Alotaibi, M.H.; Hegazy, A.S.; Kariuki, B.M.

doi:10.1107/S2414314618000366

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180036

https://doi.org/10.1107/S2414314618000366

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4-(4-Bromophenyl)-2-(3-(4-chlorophenyl)-5-{3-[5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-dihydro-1H-pyrazol-1-yl)thiazole

Gamal A. El-Hiti,^a ^* Hanan A. Mohamed,^b Bakr F. Abdel-Wahab,^b,^c Mohammad Hayal Alotaibi,^d Amany S. Hegazy ^e and Benson M. Kariuki ^e ‡

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bDepartment of Chemistry, College of Science and Humanities, Shaqra University, Duwadimi, Saudi Arabia, ^cApplied Organic Chemistry Department, National Research Centre, Dokki, Giza, Egypt, ^dNational Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia, and ^eSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 23 December 2017; accepted 6 January 2018; online 12 January 2018)

In the title compound, C₃₇H₂₈BrClN₈O, the linked chlorophenyl, pyrazolyl and thiazolyl ringss are almost coplanar, with dihedral angles of 0.6 (3)° between the chlorophenyl and pyrazolyl rings and 5.4 (3)° between the pyrazolyl and thiazolyl rings. The dihedral angle between the thiazolyl and bromophenyl rings is 17.5 (2)°. The central pyrazolyl rings subtend a dihedral angle of 67.7 (1)°. In the crystal, π–π and C—H⋯Br interactions link the molecules to form columns parallel to [010]. The π–π interactions involve partially overlapping nonparallel bromophenyl and tolyl groups.

Keywords: crystal structure; π–π stacking; heterocycles.

CCDC reference: 1815108

Structure description

Various procedures have been reported for the synthesis of heterocycles containing the pyrazolinylthiazole moiety (Abdel-Wahab et al., 2009 ; Abid & Azam, 2006 ; Bonacorso et al., 2002 ). Both pyrazolyltriazoles and 1-thiazol-2-ylpyrazolines show various antimicrobial (Abdel-Wahab et al., 2012 , 2017 ), antitumor and antimycobacterial activities (Kumar et al., 2003 ).

The asymmetric unit comprises a single molecule of C₃₇H₂₈BrClN₈O (Fig. 1). Contact between neighbouring molecules includes π–π and C—H⋯Br interactions (Table 1, Fig. 2) to form columns parallel to [010]. The π–π interactions involve partially overlapping bromophenyl and tolyl groups with a centroid-to-centroid distance of 3.993 (2) Å. The planes of the two groups are not parallel, however, with an interplanar angle of ca 15°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Br1ⁱ	0.93	2.85	3.726 (4)	157
Symmetry code: (i) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
An ORTEP representation of the title molecule showing 50% probability ellipsoids.

Figure 2
Part of the crystal structure showing intermolecular interactions as dotted lines.

Synthesis and crystallization

4-(4-Bromophenyl)-2-(3-(4-chlorophenyl)-5-{3-[5-methyl-1-(4-tolyl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-dihydro-1H-pyrazol-1-yl)thiazole was synthesized in 83% yield from reaction of 3-(4-chlorophenyl)-5-{3-[5-methyl-1-(4-tolyl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-dihydro-1H-pyrazole-1-carbothioamide and 2-bromo-1-(4-bromophenyl)ethanone in ethanol under reflux for 2 h. Colourless crystals (m.p. 279–281°C, lit. 279–281°C; Abdel-Wahab et al., 2017) were obtained by recrystallization of the crude product obtained following work-up using dimethylformamide as the solvent.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₃₇H₂₈BrClN₈S
M_r	732.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.4220 (7), 13.4232 (5), 23.8943 (14)
β (°)	90.198 (6)
V (Å³)	3342.7 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.41
Crystal size (mm)	0.42 × 0.10 × 0.04

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.794, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15250, 7792, 3958
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.702

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.183, 1.03
No. of reflections	7792
No. of parameters	435
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.95
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2008), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1815108

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618000366/xu4033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000366/xu4033Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000366/xu4033Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

4-(4-Bromophenyl)-2-(3-(4-chlorophenyl)-5-{3-[5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl]-1-phenyl-1H-pyrazol-4-yl}-4,5-dihydro-1H-pyrazol-1-yl)thiazole top

Crystal data top

C₃₇H₂₈BrClN₈S	F(000) = 1496
M_r = 732.09	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.4220 (7) Å	Cell parameters from 2941 reflections
b = 13.4232 (5) Å	θ = 3.5–23.9°
c = 23.8943 (14) Å	µ = 1.41 mm⁻¹
β = 90.198 (6)°	T = 296 K
V = 3342.7 (3) Å³	Needle, colourless
Z = 4	0.42 × 0.10 × 0.04 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	3958 reflections with I > 2σ(I)
ω scans	R_int = 0.039
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	θ_max = 29.9°, θ_min = 3.0°
T_min = 0.794, T_max = 1.000	h = −13→13
15250 measured reflections	k = −18→13
7792 independent reflections	l = −32→24

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.183	w = 1/[σ²(F_o²) + (0.0663P)² + 2.0474P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
7792 reflections	Δρ_max = 0.77 e Å⁻³
435 parameters	Δρ_min = −0.95 e Å⁻³

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.

Refinement. Non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in calculated positions and refined using a riding model. Methine C—H bonds were fixed at 0.98 Å, with displacement parameters 1.2 times U_eq(C). Ethyl C—H bonds were fixed at 0.97 Å, with displacement parameters 1.2 times U_eq(C). Methyl C—H bonds were fixed at 0.96 Å, with displacement parameters 1.5 times U_eq(C), and were allowed to spin about the C—C bond. Aromatic C—H distances were set to 0.93 Å and their U_iso(H) set to 1.2 times the U_eq(C).

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

	x	y	z	U_iso*/U_eq
C1	−0.0099 (4)	0.4942 (3)	0.33097 (16)	0.0498 (9)
C2	−0.0953 (4)	0.5332 (3)	0.29246 (18)	0.0607 (11)
H2	−0.0901	0.6003	0.2831	0.073*
C3	−0.1882 (4)	0.4747 (3)	0.26767 (19)	0.0688 (12)
H3	−0.2451	0.5022	0.2419	0.083*
C4	−0.1960 (4)	0.3762 (3)	0.28134 (19)	0.0623 (11)
C5	−0.1140 (4)	0.3358 (3)	0.3204 (2)	0.0648 (12)
H5	−0.1209	0.2689	0.3300	0.078*
C6	−0.0220 (4)	0.3943 (3)	0.34518 (18)	0.0581 (11)
H6	0.0328	0.3668	0.3718	0.070*
C7	0.0919 (4)	0.5579 (3)	0.35531 (16)	0.0491 (9)
C8	0.1620 (4)	0.5379 (3)	0.40160 (18)	0.0597 (11)
H8	0.1527	0.4810	0.4234	0.072*
C9	0.2136 (4)	0.6910 (3)	0.35524 (15)	0.0482 (9)
C10	0.3825 (4)	0.9098 (3)	0.34920 (16)	0.0474 (9)
C11	0.3075 (4)	0.9318 (3)	0.29734 (16)	0.0568 (11)
H11A	0.3638	0.9422	0.2657	0.068*
H11B	0.2542	0.9903	0.3022	0.068*
C12	0.2252 (4)	0.8382 (3)	0.28926 (15)	0.0487 (9)
H12	0.1340	0.8544	0.2931	0.058*
C13	0.4759 (4)	0.9774 (3)	0.37459 (16)	0.0501 (9)
C14	0.5408 (4)	0.9515 (3)	0.4233 (2)	0.0715 (13)
H14	0.5252	0.8899	0.4399	0.086*
C15	0.6282 (5)	1.0159 (3)	0.4476 (2)	0.0831 (15)
H15	0.6713	0.9978	0.4802	0.100*
C16	0.6511 (4)	1.1068 (3)	0.4232 (2)	0.0659 (12)
C17	0.5883 (5)	1.1349 (3)	0.37556 (19)	0.0679 (12)
H17	0.6047	1.1966	0.3593	0.082*
C18	0.4996 (4)	1.0703 (3)	0.35153 (18)	0.0611 (11)
H18	0.4555	1.0898	0.3195	0.073*
C19	0.2493 (4)	0.7877 (2)	0.23490 (15)	0.0440 (8)
C20	0.3277 (4)	0.7084 (2)	0.22460 (15)	0.0471 (9)
H20	0.3740	0.6728	0.2513	0.057*
C21	0.2008 (4)	0.8139 (2)	0.18121 (15)	0.0449 (9)
C22	0.3920 (4)	0.6132 (2)	0.13991 (15)	0.0469 (9)
C23	0.3448 (4)	0.5813 (3)	0.08881 (17)	0.0611 (11)
H23	0.2739	0.6121	0.0726	0.073*
C24	0.4049 (5)	0.5027 (4)	0.0624 (2)	0.0838 (15)
H24	0.3743	0.4800	0.0281	0.101*
C25	0.5106 (5)	0.4577 (4)	0.0869 (2)	0.0829 (15)
H25	0.5501	0.4043	0.0691	0.099*
C26	0.5570 (5)	0.4910 (3)	0.1368 (2)	0.0729 (13)
H26	0.6286	0.4609	0.1528	0.087*
C27	0.4981 (4)	0.5691 (3)	0.16364 (17)	0.0568 (10)
H27	0.5299	0.5919	0.1977	0.068*
C28	0.1107 (4)	0.8942 (3)	0.16787 (15)	0.0456 (9)
C29	0.0411 (4)	0.9133 (3)	0.12035 (15)	0.0457 (9)
C30	0.0442 (4)	0.8669 (3)	0.06355 (16)	0.0575 (10)
H30A	−0.0321	0.8280	0.0579	0.086*
H30B	0.1182	0.8247	0.0606	0.086*
H30C	0.0483	0.9183	0.0357	0.086*
C31	−0.1280 (4)	1.0448 (3)	0.10234 (15)	0.0468 (9)
C32	−0.1308 (4)	1.1480 (3)	0.10141 (19)	0.0610 (11)
H32	−0.0677	1.1848	0.1197	0.073*
C33	−0.2283 (4)	1.1950 (3)	0.0731 (2)	0.0637 (12)
H33	−0.2305	1.2642	0.0729	0.076*
C34	−0.3234 (4)	1.1431 (3)	0.04488 (16)	0.0522 (9)
C35	−0.3173 (4)	1.0401 (3)	0.04686 (16)	0.0509 (9)
H35	−0.3799	1.0029	0.0285	0.061*
C36	−0.2212 (4)	0.9914 (3)	0.07533 (16)	0.0496 (9)
H36	−0.2195	0.9222	0.0762	0.060*
C37	−0.4290 (4)	1.1953 (3)	0.0139 (2)	0.0728 (13)
H37A	−0.4940	1.2158	0.0398	0.109*
H37B	−0.4657	1.1509	−0.0133	0.109*
H37C	−0.3949	1.2528	−0.0048	0.109*
N1	0.1209 (3)	0.6470 (2)	0.32887 (13)	0.0504 (8)
N2	0.2693 (3)	0.7769 (2)	0.33713 (13)	0.0543 (8)
N3	0.3588 (3)	0.8233 (2)	0.37024 (13)	0.0518 (8)
N4	0.3263 (3)	0.6905 (2)	0.16892 (12)	0.0453 (7)
N5	0.2478 (3)	0.7548 (2)	0.14118 (12)	0.0476 (7)
N7	0.0817 (3)	0.9641 (2)	0.20710 (13)	0.0566 (8)
N8	−0.0038 (3)	1.0250 (2)	0.18692 (14)	0.0565 (8)
N9	−0.0303 (3)	0.9945 (2)	0.13380 (13)	0.0475 (7)
Cl1	0.76129 (15)	1.18779 (9)	0.45379 (7)	0.1031 (5)
S1	0.27060 (11)	0.63119 (8)	0.41492 (5)	0.0611 (3)
Br1	−0.31987 (7)	0.29441 (4)	0.24515 (3)	0.1046 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.053 (2)	0.0446 (19)	0.052 (2)	0.0050 (17)	0.0076 (19)	0.0015 (17)
C2	0.068 (3)	0.044 (2)	0.070 (3)	−0.0030 (19)	−0.008 (2)	0.011 (2)
C3	0.077 (3)	0.053 (2)	0.075 (3)	−0.008 (2)	−0.022 (3)	0.011 (2)
C4	0.069 (3)	0.046 (2)	0.072 (3)	−0.0075 (19)	0.000 (2)	0.000 (2)
C5	0.070 (3)	0.0405 (19)	0.084 (3)	0.000 (2)	0.003 (3)	0.003 (2)
C6	0.056 (3)	0.050 (2)	0.069 (3)	0.0066 (19)	0.005 (2)	0.010 (2)
C7	0.049 (2)	0.0468 (19)	0.051 (2)	0.0057 (17)	0.0093 (19)	0.0021 (17)
C8	0.061 (3)	0.061 (2)	0.058 (3)	−0.004 (2)	−0.001 (2)	0.016 (2)
C9	0.053 (3)	0.051 (2)	0.041 (2)	0.0031 (18)	0.0031 (19)	−0.0026 (17)
C10	0.048 (2)	0.0457 (19)	0.048 (2)	0.0051 (17)	0.0010 (18)	−0.0052 (17)
C11	0.082 (3)	0.0433 (19)	0.045 (2)	0.0012 (19)	−0.008 (2)	−0.0041 (17)
C12	0.058 (2)	0.0469 (19)	0.041 (2)	0.0005 (17)	−0.0014 (18)	−0.0009 (16)
C13	0.053 (2)	0.048 (2)	0.049 (2)	0.0027 (17)	0.0001 (19)	−0.0025 (17)
C14	0.072 (3)	0.060 (2)	0.083 (3)	−0.008 (2)	−0.023 (3)	0.014 (2)
C15	0.078 (4)	0.075 (3)	0.096 (4)	−0.007 (3)	−0.038 (3)	0.011 (3)
C16	0.058 (3)	0.059 (2)	0.081 (3)	−0.005 (2)	−0.013 (2)	−0.005 (2)
C17	0.083 (3)	0.049 (2)	0.071 (3)	−0.006 (2)	−0.002 (3)	−0.002 (2)
C18	0.076 (3)	0.051 (2)	0.056 (2)	−0.001 (2)	−0.008 (2)	−0.0019 (19)
C19	0.050 (2)	0.0399 (17)	0.042 (2)	−0.0033 (16)	−0.0040 (17)	−0.0016 (15)
C20	0.059 (3)	0.0429 (19)	0.039 (2)	−0.0002 (17)	−0.0070 (18)	−0.0001 (15)
C21	0.046 (2)	0.0449 (18)	0.044 (2)	−0.0017 (16)	−0.0061 (17)	−0.0042 (16)
C22	0.052 (2)	0.0425 (18)	0.046 (2)	0.0005 (17)	0.0034 (18)	−0.0008 (16)
C23	0.061 (3)	0.070 (3)	0.052 (2)	0.004 (2)	−0.006 (2)	−0.014 (2)
C24	0.092 (4)	0.097 (3)	0.063 (3)	0.013 (3)	−0.014 (3)	−0.035 (3)
C25	0.096 (4)	0.074 (3)	0.079 (4)	0.026 (3)	0.003 (3)	−0.021 (3)
C26	0.088 (4)	0.067 (3)	0.063 (3)	0.025 (2)	−0.002 (3)	−0.006 (2)
C27	0.066 (3)	0.054 (2)	0.050 (2)	0.008 (2)	−0.006 (2)	−0.0020 (19)
C28	0.046 (2)	0.0460 (18)	0.044 (2)	0.0007 (16)	−0.0041 (17)	−0.0040 (16)
C29	0.047 (2)	0.0441 (18)	0.046 (2)	0.0012 (16)	−0.0046 (18)	−0.0011 (16)
C30	0.067 (3)	0.062 (2)	0.044 (2)	0.009 (2)	−0.004 (2)	−0.0053 (19)
C31	0.048 (2)	0.0485 (19)	0.044 (2)	0.0026 (17)	−0.0044 (18)	−0.0001 (17)
C32	0.055 (3)	0.049 (2)	0.079 (3)	0.0033 (19)	−0.019 (2)	−0.009 (2)
C33	0.064 (3)	0.041 (2)	0.085 (3)	0.0061 (19)	−0.009 (2)	−0.002 (2)
C34	0.051 (2)	0.052 (2)	0.054 (2)	0.0030 (18)	−0.0045 (19)	0.0001 (18)
C35	0.051 (2)	0.051 (2)	0.051 (2)	−0.0030 (18)	−0.0098 (19)	0.0009 (18)
C36	0.053 (2)	0.0419 (18)	0.054 (2)	−0.0043 (17)	−0.0038 (19)	0.0031 (17)
C37	0.068 (3)	0.061 (3)	0.089 (3)	0.012 (2)	−0.022 (3)	0.003 (2)
N1	0.061 (2)	0.0459 (16)	0.0442 (18)	−0.0017 (15)	−0.0005 (16)	0.0034 (14)
N2	0.068 (2)	0.0512 (17)	0.0442 (18)	−0.0110 (16)	−0.0103 (17)	0.0055 (15)
N3	0.057 (2)	0.0542 (18)	0.0445 (18)	−0.0003 (15)	−0.0053 (16)	−0.0008 (15)
N4	0.053 (2)	0.0412 (15)	0.0418 (17)	0.0041 (13)	−0.0021 (15)	−0.0017 (13)
N5	0.054 (2)	0.0466 (16)	0.0424 (17)	0.0032 (14)	−0.0062 (15)	−0.0001 (14)
N7	0.061 (2)	0.0561 (18)	0.053 (2)	0.0097 (16)	−0.0135 (17)	−0.0093 (16)
N8	0.060 (2)	0.0588 (19)	0.051 (2)	0.0098 (16)	−0.0119 (16)	−0.0110 (16)
N9	0.0463 (19)	0.0486 (16)	0.0476 (18)	0.0028 (14)	−0.0072 (15)	−0.0050 (14)
Cl1	0.1052 (12)	0.0701 (7)	0.1337 (13)	−0.0203 (7)	−0.0471 (10)	−0.0058 (8)
S1	0.0605 (7)	0.0698 (6)	0.0529 (6)	−0.0044 (5)	−0.0073 (5)	0.0115 (5)
Br1	0.1295 (6)	0.0716 (3)	0.1125 (5)	−0.0373 (3)	−0.0330 (4)	0.0029 (3)

Geometric parameters (Å, º) top

C1—C2	1.381 (5)	C20—H20	0.9300
C1—C6	1.389 (5)	C21—N5	1.336 (4)
C1—C7	1.481 (5)	C21—C28	1.464 (5)
C2—C3	1.378 (6)	C22—C27	1.375 (5)
C2—H2	0.9300	C22—C23	1.383 (5)
C3—C4	1.365 (6)	C22—N4	1.424 (4)
C3—H3	0.9300	C23—C24	1.380 (6)
C4—C5	1.375 (6)	C23—H23	0.9300
C4—Br1	1.900 (4)	C24—C25	1.384 (6)
C5—C6	1.372 (6)	C24—H24	0.9300
C5—H5	0.9300	C25—C26	1.361 (6)
C6—H6	0.9300	C25—H25	0.9300
C7—C8	1.351 (5)	C26—C27	1.374 (6)
C7—N1	1.386 (5)	C26—H26	0.9300
C8—S1	1.717 (4)	C27—H27	0.9300
C8—H8	0.9300	C28—N7	1.361 (4)
C9—N1	1.295 (5)	C28—C29	1.370 (5)
C9—N2	1.362 (5)	C29—N9	1.360 (4)
C9—S1	1.739 (4)	C29—C30	1.493 (5)
C10—N3	1.289 (5)	C30—H30A	0.9600
C10—C13	1.461 (5)	C30—H30B	0.9600
C10—C11	1.493 (5)	C30—H30C	0.9600
C11—C12	1.532 (5)	C31—C36	1.367 (5)
C11—H11A	0.9700	C31—C32	1.385 (5)
C11—H11B	0.9700	C31—N9	1.433 (5)
C12—N2	1.481 (5)	C32—C33	1.372 (6)
C12—C19	1.487 (5)	C32—H32	0.9300
C12—H12	0.9800	C33—C34	1.385 (6)
C13—C18	1.387 (5)	C33—H33	0.9300
C13—C14	1.389 (6)	C34—C35	1.386 (5)
C14—C15	1.382 (6)	C34—C37	1.499 (5)
C14—H14	0.9300	C35—C36	1.374 (5)
C15—C16	1.373 (6)	C35—H35	0.9300
C15—H15	0.9300	C36—H36	0.9300
C16—C17	1.365 (6)	C37—H37A	0.9600
C16—Cl1	1.740 (4)	C37—H37B	0.9600
C17—C18	1.390 (6)	C37—H37C	0.9600
C17—H17	0.9300	N2—N3	1.371 (4)
C18—H18	0.9300	N4—N5	1.361 (4)
C19—C20	1.365 (5)	N7—N8	1.302 (4)
C19—C21	1.421 (5)	N8—N9	1.361 (4)
C20—N4	1.352 (4)

C2—C1—C6	118.0 (4)	C27—C22—C23	120.9 (4)
C2—C1—C7	120.1 (3)	C27—C22—N4	120.0 (3)
C6—C1—C7	121.9 (4)	C23—C22—N4	119.0 (4)
C3—C2—C1	121.4 (4)	C24—C23—C22	118.7 (4)
C3—C2—H2	119.3	C24—C23—H23	120.7
C1—C2—H2	119.3	C22—C23—H23	120.7
C4—C3—C2	119.4 (4)	C23—C24—C25	120.1 (4)
C4—C3—H3	120.3	C23—C24—H24	119.9
C2—C3—H3	120.3	C25—C24—H24	119.9
C3—C4—C5	120.4 (4)	C26—C25—C24	120.4 (4)
C3—C4—Br1	119.5 (4)	C26—C25—H25	119.8
C5—C4—Br1	120.1 (3)	C24—C25—H25	119.8
C6—C5—C4	120.0 (4)	C25—C26—C27	120.1 (4)
C6—C5—H5	120.0	C25—C26—H26	119.9
C4—C5—H5	120.0	C27—C26—H26	119.9
C5—C6—C1	120.7 (4)	C26—C27—C22	119.7 (4)
C5—C6—H6	119.6	C26—C27—H27	120.1
C1—C6—H6	119.6	C22—C27—H27	120.1
C8—C7—N1	115.3 (4)	N7—C28—C29	108.9 (3)
C8—C7—C1	126.2 (3)	N7—C28—C21	120.1 (3)
N1—C7—C1	118.5 (3)	C29—C28—C21	131.0 (3)
C7—C8—S1	111.1 (3)	N9—C29—C28	104.0 (3)
C7—C8—H8	124.4	N9—C29—C30	124.2 (3)
S1—C8—H8	124.4	C28—C29—C30	131.5 (3)
N1—C9—N2	123.3 (3)	C29—C30—H30A	109.5
N1—C9—S1	116.1 (3)	C29—C30—H30B	109.5
N2—C9—S1	120.5 (3)	H30A—C30—H30B	109.5
N3—C10—C13	121.7 (3)	C29—C30—H30C	109.5
N3—C10—C11	113.7 (3)	H30A—C30—H30C	109.5
C13—C10—C11	124.6 (3)	H30B—C30—H30C	109.5
C10—C11—C12	103.5 (3)	C36—C31—C32	120.1 (4)
C10—C11—H11A	111.1	C36—C31—N9	120.2 (3)
C12—C11—H11A	111.1	C32—C31—N9	119.6 (3)
C10—C11—H11B	111.1	C33—C32—C31	118.9 (4)
C12—C11—H11B	111.1	C33—C32—H32	120.5
H11A—C11—H11B	109.0	C31—C32—H32	120.5
N2—C12—C19	111.6 (3)	C32—C33—C34	122.5 (4)
N2—C12—C11	100.7 (3)	C32—C33—H33	118.8
C19—C12—C11	112.8 (3)	C34—C33—H33	118.8
N2—C12—H12	110.4	C33—C34—C35	116.9 (4)
C19—C12—H12	110.4	C33—C34—C37	122.0 (4)
C11—C12—H12	110.4	C35—C34—C37	121.1 (4)
C18—C13—C14	118.1 (4)	C36—C35—C34	121.6 (4)
C18—C13—C10	120.9 (4)	C36—C35—H35	119.2
C14—C13—C10	120.9 (4)	C34—C35—H35	119.2
C15—C14—C13	120.9 (4)	C31—C36—C35	120.0 (3)
C15—C14—H14	119.6	C31—C36—H36	120.0
C13—C14—H14	119.6	C35—C36—H36	120.0
C16—C15—C14	119.6 (4)	C34—C37—H37A	109.5
C16—C15—H15	120.2	C34—C37—H37B	109.5
C14—C15—H15	120.2	H37A—C37—H37B	109.5
C17—C16—C15	121.1 (4)	C34—C37—H37C	109.5
C17—C16—Cl1	119.4 (3)	H37A—C37—H37C	109.5
C15—C16—Cl1	119.5 (4)	H37B—C37—H37C	109.5
C16—C17—C18	119.2 (4)	C9—N1—C7	109.6 (3)
C16—C17—H17	120.4	C9—N2—N3	119.4 (3)
C18—C17—H17	120.4	C9—N2—C12	125.8 (3)
C13—C18—C17	121.1 (4)	N3—N2—C12	113.7 (3)
C13—C18—H18	119.5	C10—N3—N2	108.3 (3)
C17—C18—H18	119.5	C20—N4—N5	111.8 (3)
C20—C19—C21	104.0 (3)	C20—N4—C22	127.2 (3)
C20—C19—C12	128.0 (3)	N5—N4—C22	121.0 (3)
C21—C19—C12	128.0 (3)	C21—N5—N4	104.4 (3)
N4—C20—C19	108.2 (3)	N8—N7—C28	109.4 (3)
N4—C20—H20	125.9	N7—N8—N9	107.0 (3)
C19—C20—H20	125.9	C29—N9—N8	110.7 (3)
N5—C21—C19	111.7 (3)	C29—N9—C31	130.0 (3)
N5—C21—C28	121.1 (3)	N8—N9—C31	119.3 (3)
C19—C21—C28	127.2 (3)	C8—S1—C9	87.82 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br1ⁱ	0.93	2.85	3.726 (4)	157

Symmetry code: (i) −x−1/2, y+1/2, −z+1/2.

Footnotes

‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.

Funding information

The project was supported by King Saud University, Deanship of Scientific Research, Research Chairs.

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