5-(4-Fluoro­phen­yl)-1-[4-(4-methyl­phen­yl)thia­zol-2-yl]-3-[4-(prop-2-yn­yloxy)phen­yl]-4,5-di­hydro-1H-pyrazole

Archana, S.D.; Nagma Banu, H.A.; Kalluraya, B.; Yathirajan, H.S.; Balerao, R.; Butcher, R.J.

doi:10.1107/S2414314622010033

organic compounds

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ISSN: 2414-3146

Volume 7| Part 10| October 2022| x221003

https://doi.org/10.1107/S2414314622010033

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5-(4-Fluorophenyl)-1-[4-(4-methylphenyl)thiazol-2-yl]-3-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-1H-pyrazole

Sreeramapura D. Archana,^a Holalagudu A. Nagma Banu,^b Balakrishna Kalluraya,^b Hemmige S. Yathirajan,^a ^* Rishik Balerao ^c and Ray J. Butcher ^d

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, ^cThomas Jefferson High School for Science and Technology, 6560 Braddock Rd, Alexandria, VA 22312, USA, and ^dDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: yathirajan@hotmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 12 October 2022; accepted 13 October 2022; online 25 October 2022)

In the title compound, C₂₈H₂₂FN₃OS, four rings are almost coplanar, with the fluorophenyl ring substantially twisted. In the extended structure, aromatic π–π stacking interactions between the pyrazole ring and the tolyl ring link the molecules into centrosymmetric dimers.

Keywords: crystal structure; fluorophenyl; 4-(prop-2-ynyloxy)phenyl; pyrazole; thiazole.

CCDC reference: 2212832

Structure description

Pyrazoles and thiazoles are important scaffolds in developing target drug molecules. They are five-membered nitrogen heterocycles possessing a variety of pharmacological activities, including antibacterial (Tanitame et al., 2004 ), antifungal (Hassan, 2013 ), anti-inflammatory (Farghaly et al., 2000 ), antidepressant (Secci et al., 2011 ), anti-analgesic (Jamwal et al., 2013 ), anticancer (Keter & Darkwa, 2012 ), antitubercular (Kumar et al., 2020 ), antiviral (Rashad et al., 2008 ) and antidiabetic (Datar & Jadhav, 2014 ). The design, efficient synthesis and molecular docking of some novel thiazolyl–pyrazole derivatives as anticancer reagents have been reported (Sayed et al., 2019 ). We have recently reported the formation of 1-(thiazol-2-yl)-4,5-dihydropyrazoles from simple precursors, as the synthesis, spectroscopic characterization and the structures of an intermediate and two products (Mahesha et al., 2021 ).

A new series of 1,3-thiazole integrated pyrazoline scaffolds have been synthesized and characterized [Cambridge Structural Database (CSD; Groom et al., 2016 ) refcodes DADQIL and DADQEH; Salian et al., 2017 ]. The synthesis, fluorescence, TGA and crystal structure of a thiazolyl–pyrazoline derived from chalcones has been described (JUNRAN; Suwunwong et al., 2015 ). In addition, the following crystal structures of related compounds have been reported: 2-[3-(4-bromophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thiazole (IDOMOF; Abdel-Wahab et al., 2013c ), 2-[5-(4-fluorophenyl)-3-(4-methylphenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thiazole (MEWQUC; Abdel-Wahab et al., 2013a ), 2-[3-(4-chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thiazole (WIGQIO; Abdel-Wahab et al., 2013b ), 2-[3-(4-chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-8H-indeno[1,2-d]thiazole (WOCFEC; El-Hiti et al., 2019 ) and 2-[3-(4-bromophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-8H-indeno[1,2-d]thiazole (PUVVAG; Alotaibi et al., 2020 ).

Keeping this in mind, the present study was planned to synthesize a ring system that contains both pyrazole and thiazole in a single hybrid molecule with an acetylene substituent, which can further be modified into highly functionalized heterocycles (Larock & Yum, 1991 ; Sonogashira, 2002 ).

We now describe the synthesis and structure of the title compound, 5-(4-fluorophenyl)-1-[5-(4-methylphenyl)thiazol-2-yl]-3-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-1H-pyrazole; the molecule crystallizes in the space group P2₁/c with one molecule in the asymmetric unit (Fig. 1). The four rings that make up the central core (A: phenyl ring C7–C12, B: the five-membered ring containing atom S1, C, the five-membered ring containing atoms N1 and N2, D: phenyl ring C20–C25) are almost co-planar, the dihedral angle between A and D, which shows the overall twist, is 3.65 (7)°, that between A and B is 12.27 (7)°, that between B and C is 3.26 (5)°, and that between C and D is 0.34 (7)°. Ring C, which contains the sp³ atoms C2 and C3,is almost planar (r.m.s. deviation = 0.006 Å), which we find surprising given the potential steric interactions of the H atoms connected to C2 and C3. The fluorophenyl substituent makes a dihedral angle of 87.84 (5)° with ring C.

Figure 1
Perspective view showing the molecule and atom labelling. Intramolecular C—H⋯N interactions are shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level.

In the crystal, there are π–π interactions between rings A and C, which link the molecules into a centrosymmetric dimer (centroid–centroid distance = 3.649 Å, with a slippage of 0.765 Å; Fig. 2). In addition there are weak C—H⋯F and C—H⋯S interactions, which link the molecules into a three-dimensional array (see Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯N3	0.95	2.52	2.849 (2)	100
C16—H16⋯S1ⁱ	0.95	3.10	3.9986 (19)	159
C21—H21⋯N2	0.95	2.55	2.853 (2)	99
C22—H22⋯F1ⁱⁱ	0.95	2.53	3.245 (2)	132
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Packing diagram showing intermolecular C—H⋯S and C—H⋯F interactions, as well as intramolecular C—H⋯N interactions, as dashed lines.

Synthesis and crystallization

1-(p-Propyloxyphenyl)-3-(4-flurophenyl)prop-2-en-1-one (A) was obtained by the base-catalysed condensation of p-propylyoxyacetophenone (3 g, 0.0174 mol) with 4-flurobenzaldehyde (2.59 g, 0.020 mol) in an ethanol medium employing sodium hydroxide as catalyst. Propanone (A) (2 g, 0.0075 mol), on treatment with thiosemicarbazide (1.3 g, 0.015 mol) in alcoholic potassium hydroxide, gave 3-(4-fluorophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-pyrazole-1-carbothioamide (B).

The synthesized B (1 g, 0.002 mol) and 4-methylphenacyl bromide (0.58 g, 0.002 mol) were added to ethanol (20 ml) and heated at reflux for 1 h. After cooling, the obtained product was collected by filtration and crystallized from the mixed solvents of ethanol and dimethylformamide (DMF) (3:2 v/v). The overall reaction scheme is shown in Fig. 3.

Figure 3
Reaction scheme for the synthesis of 5-(4-fluorophenyl)-1-[5-(4-methylphenyl)thiazol-2-yl]-3-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-1H-pyrazole.

Yield: 78%; m.p. 483–485 K.. Analysis for C₂₈H₂₂FN₂OS: MS (m/z) 468.15 (M⁺ + 1). ¹H NMR (400 MHz, CDCl₃): δ 2.27 (s, 3H) 2.79 (s, 1H, triple-bonded C—H), 3.09 (dd, 1H, J_AX = 18.2, J_AB = 5.8 Hz), 3.83 (dd, 1H, J_XA = 18.6, J_XB = 13.2 Hz), 4.40 (s, 2H, O—CH₂), 5.34 (dd, 1H, J_BA = 5.8, J_BX = 12.8 Hz), 7.08 (dd, 2H, J = 8.5 Hz, Ar-H), 7.13 (dd, 2H, J = 8.1 Hz, Ar-H), 7.26 (dd, 2H, J = 8.8 Hz, Ar-H), 7.39 (dd, 2H, J = 8.5 Hz, Ar-H), 7.41 (dd, 2H, J = 8.8 Hz, Ar-H), 7.69 (dd, 2H, J = 8.1 Hz, Ar-H), 8.09 (s, 1H-thiazole-H).

Refinement

Crystal data, data collection and structure refinement details for the title compound are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₈H₂₂FN₃OS
M_r	467.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.7859 (13), 14.5638 (16), 14.9956 (14)
β (°)	97.144 (3)
V (Å³)	2337.3 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.17
Crystal size (mm)	0.24 × 0.17 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.667, 0.740
No. of measured, independent and observed [I > 2σ(I)] reflections	34158, 5339, 3999
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.124, 1.05
No. of reflections	5339
No. of parameters	312
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25
Computer programs: APEX2 (Bruker, 2005 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2212832

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622010033/bt4127sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622010033/bt4127Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622010033/bt4127Isup3.cml

checkCIF report

Computing details top

Data collection: APEX 2 (Bruker, 2005); cell refinement: APEX 2 (Bruker, 2005); data reduction: APEX 2 (Bruker, 2005); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

5-(4-Fluorophenyl)-1-[4-(4-methylphenyl)thiazol-2-yl]-3-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-1H-pyrazole top

Crystal data top

C₂₈H₂₂FN₃OS	F(000) = 976
M_r = 467.54	D_x = 1.329 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.7859 (13) Å	Cell parameters from 8134 reflections
b = 14.5638 (16) Å	θ = 2.3–19.4°
c = 14.9956 (14) Å	µ = 0.17 mm⁻¹
β = 97.144 (3)°	T = 100 K
V = 2337.3 (4) Å³	Prism, pale yellow
Z = 4	0.24 × 0.17 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	3999 reflections with I > 2σ(I)
ω & φ scans	R_int = 0.055
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θ_max = 27.5°, θ_min = 2.4°
T_min = 0.667, T_max = 0.740	h = −13→13
34158 measured reflections	k = −18→18
5339 independent reflections	l = −19→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0555P)² + 0.4922P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5339 reflections	Δρ_max = 0.21 e Å⁻³
312 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints

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
S1	0.41974 (4)	0.50137 (3)	0.68772 (3)	0.05135 (14)
F1	0.30040 (14)	0.00083 (9)	0.45510 (11)	0.0947 (5)
O1	1.05115 (12)	0.28517 (9)	1.05004 (8)	0.0620 (4)
N1	0.55591 (13)	0.35607 (10)	0.64338 (9)	0.0504 (3)
N2	0.62314 (12)	0.36498 (9)	0.72765 (9)	0.0458 (3)
N3	0.40086 (11)	0.41449 (9)	0.53590 (9)	0.0416 (3)
C1	0.71955 (14)	0.31161 (11)	0.73107 (11)	0.0429 (4)
C2	0.72870 (16)	0.25989 (13)	0.64542 (11)	0.0519 (4)
H2A	0.725916	0.192751	0.655328	0.062*
H2B	0.806651	0.275473	0.620224	0.062*
C3	0.61252 (15)	0.29284 (11)	0.58290 (11)	0.0453 (4)
H3	0.639256	0.327907	0.531225	0.054*
C4	0.46340 (14)	0.41667 (10)	0.61583 (11)	0.0421 (3)
C5	0.30581 (16)	0.53433 (12)	0.60280 (11)	0.0501 (4)
H5	0.248195	0.582902	0.607499	0.060*
C6	0.30918 (15)	0.48190 (10)	0.52848 (11)	0.0415 (3)
C7	0.22498 (15)	0.48815 (10)	0.44307 (11)	0.0428 (4)
C8	0.11627 (19)	0.53946 (15)	0.43594 (13)	0.0641 (5)
H8	0.096611	0.573810	0.486179	0.077*
C9	0.0357 (2)	0.54138 (16)	0.35642 (14)	0.0711 (6)
H9	−0.038797	0.576647	0.353696	0.085*
C10	0.06012 (18)	0.49389 (12)	0.28146 (12)	0.0542 (4)
C11	0.16914 (18)	0.44361 (13)	0.28824 (12)	0.0554 (4)
H11	0.189312	0.410573	0.237352	0.066*
C12	0.25025 (16)	0.44011 (12)	0.36778 (11)	0.0499 (4)
H12	0.324148	0.404195	0.370509	0.060*
C13	−0.0308 (2)	0.49575 (16)	0.19603 (14)	0.0742 (6)
H13A	−0.115982	0.487080	0.210809	0.111*
H13B	−0.010253	0.446321	0.156014	0.111*
H13C	−0.024930	0.555058	0.165965	0.111*
C14	0.52458 (14)	0.21655 (11)	0.54827 (10)	0.0417 (3)
C15	0.50313 (16)	0.19735 (12)	0.45752 (11)	0.0513 (4)
H15	0.540276	0.234834	0.416283	0.062*
C16	0.42798 (18)	0.12400 (13)	0.42561 (13)	0.0605 (5)
H16	0.414806	0.109938	0.363286	0.073*
C17	0.37364 (18)	0.07275 (13)	0.48627 (15)	0.0615 (5)
C18	0.3914 (2)	0.08969 (13)	0.57641 (15)	0.0645 (5)
H18	0.352303	0.052768	0.617046	0.077*
C19	0.46802 (17)	0.16219 (12)	0.60694 (12)	0.0537 (4)
H19	0.481996	0.174834	0.669533	0.064*
C20	0.80833 (14)	0.30375 (11)	0.81275 (10)	0.0425 (3)
C21	0.79227 (15)	0.35436 (12)	0.88945 (11)	0.0484 (4)
H21	0.722761	0.394575	0.888410	0.058*
C22	0.87487 (16)	0.34712 (13)	0.96621 (11)	0.0515 (4)
H22	0.862460	0.382276	1.017719	0.062*
C23	0.97723 (15)	0.28819 (12)	0.96889 (11)	0.0459 (4)
C24	0.99600 (16)	0.23779 (12)	0.89378 (11)	0.0503 (4)
H24	1.065768	0.197771	0.895145	0.060*
C25	0.91183 (15)	0.24615 (12)	0.81614 (11)	0.0493 (4)
H25	0.925194	0.211853	0.764298	0.059*
C26	1.15665 (16)	0.22557 (13)	1.05765 (11)	0.0520 (4)
H26A	1.221624	0.250122	1.022969	0.062*
H26B	1.131967	0.163786	1.034290	0.062*
C27	1.20376 (17)	0.22073 (13)	1.15271 (12)	0.0553 (4)
C28	1.2393 (2)	0.21588 (18)	1.22951 (16)	0.0804 (7)
H28	1.256 (3)	0.209 (2)	1.2914 (19)	0.121 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0563 (3)	0.0476 (2)	0.0466 (2)	0.00514 (19)	−0.00782 (18)	−0.00366 (18)
F1	0.0895 (9)	0.0677 (8)	0.1199 (12)	−0.0298 (7)	−0.0144 (8)	−0.0172 (7)
O1	0.0650 (8)	0.0700 (8)	0.0460 (7)	0.0306 (7)	−0.0132 (6)	−0.0083 (6)
N1	0.0508 (8)	0.0449 (8)	0.0497 (8)	0.0081 (6)	−0.0162 (6)	−0.0063 (6)
N2	0.0465 (7)	0.0418 (7)	0.0454 (7)	0.0022 (6)	−0.0085 (6)	−0.0006 (6)
N3	0.0399 (7)	0.0379 (7)	0.0445 (7)	−0.0016 (5)	−0.0049 (5)	0.0027 (5)
C1	0.0404 (8)	0.0409 (8)	0.0454 (9)	−0.0008 (6)	−0.0026 (6)	0.0003 (7)
C2	0.0448 (9)	0.0569 (10)	0.0511 (10)	0.0043 (8)	−0.0060 (7)	−0.0070 (8)
C3	0.0450 (8)	0.0438 (9)	0.0447 (9)	0.0004 (7)	−0.0039 (7)	−0.0011 (7)
C4	0.0401 (8)	0.0359 (8)	0.0477 (9)	−0.0024 (6)	−0.0045 (6)	0.0026 (6)
C5	0.0523 (9)	0.0466 (9)	0.0487 (10)	0.0080 (8)	−0.0042 (7)	0.0019 (7)
C6	0.0406 (8)	0.0371 (8)	0.0454 (8)	−0.0012 (6)	−0.0003 (6)	0.0063 (6)
C7	0.0427 (8)	0.0383 (8)	0.0458 (9)	−0.0022 (6)	−0.0012 (7)	0.0060 (6)
C8	0.0623 (11)	0.0692 (12)	0.0569 (11)	0.0230 (10)	−0.0086 (9)	−0.0102 (9)
C9	0.0638 (12)	0.0771 (14)	0.0658 (13)	0.0250 (11)	−0.0178 (10)	−0.0050 (11)
C10	0.0587 (10)	0.0510 (10)	0.0489 (10)	−0.0079 (8)	−0.0096 (8)	0.0093 (8)
C11	0.0636 (11)	0.0578 (11)	0.0435 (9)	−0.0051 (9)	0.0017 (8)	0.0012 (8)
C12	0.0483 (9)	0.0517 (10)	0.0488 (9)	0.0014 (7)	0.0032 (7)	0.0040 (7)
C13	0.0806 (15)	0.0761 (14)	0.0581 (12)	−0.0112 (11)	−0.0225 (10)	0.0095 (10)
C14	0.0432 (8)	0.0388 (8)	0.0408 (8)	0.0043 (6)	−0.0039 (6)	0.0010 (6)
C15	0.0566 (10)	0.0523 (10)	0.0425 (9)	−0.0013 (8)	−0.0036 (7)	0.0028 (7)
C16	0.0681 (12)	0.0584 (11)	0.0489 (10)	0.0040 (9)	−0.0161 (9)	−0.0086 (8)
C17	0.0570 (11)	0.0439 (10)	0.0800 (14)	−0.0070 (8)	−0.0058 (10)	−0.0063 (9)
C18	0.0711 (12)	0.0482 (10)	0.0755 (13)	−0.0109 (9)	0.0145 (10)	0.0017 (9)
C19	0.0651 (11)	0.0480 (9)	0.0475 (10)	−0.0006 (8)	0.0052 (8)	0.0003 (7)
C20	0.0396 (8)	0.0431 (8)	0.0429 (8)	0.0008 (6)	−0.0021 (6)	0.0016 (6)
C21	0.0442 (8)	0.0516 (9)	0.0474 (9)	0.0145 (7)	−0.0021 (7)	−0.0003 (7)
C22	0.0535 (9)	0.0570 (10)	0.0427 (9)	0.0163 (8)	0.0001 (7)	−0.0055 (7)
C23	0.0458 (8)	0.0488 (9)	0.0407 (8)	0.0091 (7)	−0.0041 (6)	0.0016 (7)
C24	0.0450 (9)	0.0550 (10)	0.0488 (9)	0.0161 (8)	−0.0026 (7)	−0.0037 (8)
C25	0.0482 (9)	0.0518 (10)	0.0458 (9)	0.0094 (7)	−0.0020 (7)	−0.0072 (7)
C26	0.0464 (9)	0.0547 (10)	0.0517 (10)	0.0109 (8)	−0.0064 (7)	0.0000 (8)
C27	0.0515 (10)	0.0570 (10)	0.0539 (11)	0.0114 (8)	−0.0068 (8)	0.0014 (8)
C28	0.0879 (16)	0.0896 (17)	0.0579 (14)	0.0258 (13)	−0.0137 (11)	0.0045 (12)

Geometric parameters (Å, º) top

S1—C4	1.7412 (17)	C11—C12	1.390 (2)
S1—C5	1.7241 (17)	C12—H12	0.9500
F1—C17	1.359 (2)	C13—H13A	0.9800
O1—C23	1.3701 (19)	C13—H13B	0.9800
O1—C26	1.4243 (19)	C13—H13C	0.9800
N1—N2	1.3827 (17)	C14—C15	1.380 (2)
N1—C3	1.477 (2)	C14—C19	1.381 (2)
N1—C4	1.357 (2)	C15—H15	0.9500
N2—C1	1.294 (2)	C15—C16	1.390 (2)
N3—C4	1.3005 (19)	C16—H16	0.9500
N3—C6	1.388 (2)	C16—C17	1.364 (3)
C1—C2	1.503 (2)	C17—C18	1.364 (3)
C1—C20	1.462 (2)	C18—H18	0.9500
C2—H2A	0.9900	C18—C19	1.383 (3)
C2—H2B	0.9900	C19—H19	0.9500
C2—C3	1.545 (2)	C20—C21	1.395 (2)
C3—H3	1.0000	C20—C25	1.392 (2)
C3—C14	1.510 (2)	C21—H21	0.9500
C5—H5	0.9500	C21—C22	1.369 (2)
C5—C6	1.355 (2)	C22—H22	0.9500
C6—C7	1.478 (2)	C22—C23	1.395 (2)
C7—C8	1.383 (2)	C23—C24	1.380 (2)
C7—C12	1.384 (2)	C24—H24	0.9500
C8—H8	0.9500	C24—C25	1.390 (2)
C8—C9	1.386 (3)	C25—H25	0.9500
C9—H9	0.9500	C26—H26A	0.9900
C9—C10	1.373 (3)	C26—H26B	0.9900
C10—C11	1.378 (3)	C26—C27	1.454 (2)
C10—C13	1.513 (2)	C27—C28	1.170 (3)
C11—H11	0.9500	C28—H28	0.93 (3)

C5—S1—C4	87.87 (8)	C10—C13—H13B	109.5
C23—O1—C26	117.49 (13)	C10—C13—H13C	109.5
N2—N1—C3	114.19 (12)	H13A—C13—H13B	109.5
C4—N1—N2	119.95 (13)	H13A—C13—H13C	109.5
C4—N1—C3	124.26 (13)	H13B—C13—H13C	109.5
C1—N2—N1	107.90 (13)	C15—C14—C3	120.60 (15)
C4—N3—C6	109.84 (13)	C15—C14—C19	118.61 (15)
N2—C1—C2	113.90 (13)	C19—C14—C3	120.74 (14)
N2—C1—C20	121.29 (14)	C14—C15—H15	119.5
C20—C1—C2	124.81 (14)	C14—C15—C16	120.95 (17)
C1—C2—H2A	111.1	C16—C15—H15	119.5
C1—C2—H2B	111.1	C15—C16—H16	120.9
C1—C2—C3	103.20 (13)	C17—C16—C15	118.14 (17)
H2A—C2—H2B	109.1	C17—C16—H16	120.9
C3—C2—H2A	111.1	F1—C17—C16	118.16 (19)
C3—C2—H2B	111.1	F1—C17—C18	118.96 (19)
N1—C3—C2	100.79 (12)	C18—C17—C16	122.87 (17)
N1—C3—H3	109.8	C17—C18—H18	121.0
N1—C3—C14	112.32 (13)	C17—C18—C19	118.08 (18)
C2—C3—H3	109.8	C19—C18—H18	121.0
C14—C3—C2	114.04 (14)	C14—C19—C18	121.33 (17)
C14—C3—H3	109.8	C14—C19—H19	119.3
N1—C4—S1	121.16 (12)	C18—C19—H19	119.3
N3—C4—S1	116.01 (12)	C21—C20—C1	120.91 (14)
N3—C4—N1	122.82 (15)	C25—C20—C1	121.08 (14)
S1—C5—H5	124.4	C25—C20—C21	118.01 (14)
C6—C5—S1	111.16 (13)	C20—C21—H21	119.4
C6—C5—H5	124.4	C22—C21—C20	121.19 (15)
N3—C6—C7	117.90 (14)	C22—C21—H21	119.4
C5—C6—N3	115.10 (14)	C21—C22—H22	119.9
C5—C6—C7	126.98 (15)	C21—C22—C23	120.10 (15)
C8—C7—C6	121.59 (16)	C23—C22—H22	119.9
C8—C7—C12	117.46 (16)	O1—C23—C22	114.61 (14)
C12—C7—C6	120.92 (15)	O1—C23—C24	125.41 (14)
C7—C8—H8	119.6	C24—C23—C22	119.97 (15)
C7—C8—C9	120.82 (18)	C23—C24—H24	120.3
C9—C8—H8	119.6	C23—C24—C25	119.35 (15)
C8—C9—H9	119.0	C25—C24—H24	120.3
C10—C9—C8	122.04 (18)	C20—C25—H25	119.3
C10—C9—H9	119.0	C24—C25—C20	121.37 (15)
C9—C10—C11	117.13 (16)	C24—C25—H25	119.3
C9—C10—C13	120.92 (19)	O1—C26—H26A	110.4
C11—C10—C13	121.93 (19)	O1—C26—H26B	110.4
C10—C11—H11	119.2	O1—C26—C27	106.64 (14)
C10—C11—C12	121.54 (17)	H26A—C26—H26B	108.6
C12—C11—H11	119.2	C27—C26—H26A	110.4
C7—C12—C11	120.99 (16)	C27—C26—H26B	110.4
C7—C12—H12	119.5	C28—C27—C26	178.5 (2)
C11—C12—H12	119.5	C27—C28—H28	171.9 (19)
C10—C13—H13A	109.5

S1—C5—C6—N3	0.04 (19)	C4—N3—C6—C7	−177.89 (13)
S1—C5—C6—C7	178.66 (13)	C5—S1—C4—N1	−177.59 (15)
F1—C17—C18—C19	178.88 (18)	C5—S1—C4—N3	1.24 (13)
O1—C23—C24—C25	178.61 (17)	C5—C6—C7—C8	−12.2 (3)
N1—N2—C1—C2	0.80 (19)	C5—C6—C7—C12	170.00 (17)
N1—N2—C1—C20	−178.53 (14)	C6—N3—C4—S1	−1.41 (17)
N1—C3—C14—C15	129.54 (16)	C6—N3—C4—N1	177.40 (15)
N1—C3—C14—C19	−53.1 (2)	C6—C7—C8—C9	−177.19 (18)
N2—N1—C3—C2	1.52 (18)	C6—C7—C12—C11	177.95 (15)
N2—N1—C3—C14	123.29 (14)	C7—C8—C9—C10	−0.7 (4)
N2—N1—C4—S1	−4.6 (2)	C8—C7—C12—C11	0.0 (3)
N2—N1—C4—N3	176.69 (14)	C8—C9—C10—C11	0.0 (3)
N2—C1—C2—C3	0.14 (19)	C8—C9—C10—C13	178.8 (2)
N2—C1—C20—C21	−0.6 (2)	C9—C10—C11—C12	0.8 (3)
N2—C1—C20—C25	179.91 (16)	C10—C11—C12—C7	−0.8 (3)
N3—C6—C7—C8	166.41 (17)	C12—C7—C8—C9	0.7 (3)
N3—C6—C7—C12	−11.4 (2)	C13—C10—C11—C12	−178.06 (17)
C1—C2—C3—N1	−0.93 (16)	C14—C15—C16—C17	1.5 (3)
C1—C2—C3—C14	−121.48 (15)	C15—C14—C19—C18	0.1 (3)
C1—C20—C21—C22	179.82 (16)	C15—C16—C17—F1	−179.82 (17)
C1—C20—C25—C24	−179.47 (16)	C15—C16—C17—C18	−1.0 (3)
C2—C1—C20—C21	−179.83 (16)	C16—C17—C18—C19	0.0 (3)
C2—C1—C20—C25	0.7 (3)	C17—C18—C19—C14	0.4 (3)
C2—C3—C14—C15	−116.59 (17)	C19—C14—C15—C16	−1.1 (3)
C2—C3—C14—C19	60.7 (2)	C20—C1—C2—C3	179.44 (15)
C3—N1—N2—C1	−1.52 (19)	C20—C21—C22—C23	−0.2 (3)
C3—N1—C4—S1	−169.30 (12)	C21—C20—C25—C24	1.0 (3)
C3—N1—C4—N3	11.9 (3)	C21—C22—C23—O1	−178.37 (16)
C3—C14—C15—C16	176.31 (16)	C21—C22—C23—C24	0.7 (3)
C3—C14—C19—C18	−177.27 (17)	C22—C23—C24—C25	−0.3 (3)
C4—S1—C5—C6	−0.66 (14)	C23—O1—C26—C27	−168.80 (16)
C4—N1—N2—C1	−167.73 (15)	C23—C24—C25—C20	−0.5 (3)
C4—N1—C3—C2	167.05 (15)	C25—C20—C21—C22	−0.7 (3)
C4—N1—C3—C14	−71.2 (2)	C26—O1—C23—C22	179.37 (16)
C4—N3—C6—C5	0.9 (2)	C26—O1—C23—C24	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N3	0.95	2.52	2.849 (2)	100
C16—H16···S1ⁱ	0.95	3.10	3.9986 (19)	159
C21—H21···N2	0.95	2.55	2.853 (2)	99
C22—H22···F1ⁱⁱ	0.95	2.53	3.245 (2)	132

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2.

Acknowledgements

SDA and HAN are grateful to Mysore and Mangalore Universities, respectively, for research facilities. HSY and BK are grateful to the UGC, New Delhi, for the award of BSR Faculty Fellowships.

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