Crystal structure of 4-({(1E,2E)-3-[3-(4-fluoro­phen­yl)-1-isopropyl-1H-indol-2-yl]allyl­idene}amino)-5-methyl-1H-1,2,4-triazole-5(4H)-thione

Kulkarni, A.D.; Rahman, M.L.; Mohd. Yusoff, M.; Kwong, H.C.; Quah, C.K.

doi:10.1107/S2056989015020101

research communications

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ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages 1411-1413

https://doi.org/10.1107/S2056989015020101

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Crystal structure of 4-({(1E,2E)-3-[3-(4-fluorophenyl)-1-isopropyl-1H-indol-2-yl]allylidene}amino)-5-methyl-1H-1,2,4-triazole-5(4H)-thione

Ajaykumar D. Kulkarni,^a Md. Lutfor Rahman,^b ^* Mashitah Mohd. Yusoff,^b Huey Chong Kwong ^c and Ching Kheng Quah ^d

^aDepartment of Chemistry, KLS's Gogte Institute of Technology, Jnana Ganga, Udyambag, Belagavi 590 008 Karnataka, India, ^bUniversity Malaysia Pahang, Faculty of Industrial Sciences and Technology, 26300 Gambang, Kuantan, Pahang, Malaysia, ^cSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: lutfor73@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 12 October 2015; accepted 24 October 2015; online 31 October 2015)

The title compound, C₂₃H₂₂FN₅S, exists in a trans conformation with respect to the methene C=C and the acyclic N=C bonds. The 1,2,4-triazole-5(4H)-thione ring makes dihedral angles of 88.66 (9) and 84.51 (10)°, respectively, with the indole and benzene rings. In the crystal, molecules are linked by pairs of N—H⋯S hydrogen bonds, forming inversion dimers with an R₂²(8) ring motif. The dimers are linked via C—H⋯π interactions, forming chains along [1-10]. The chains are linked via π—π interactions involving inversion-related triazole rings [centroid–centroid distance = 3.4340 (13) Å], forming layers parallel to the ab plane.

Keywords: crystal structure; 1,2,4-triazole-5(4H)-thione; indole; Schiff base; N—H⋯S hydrogen bonds; C—H⋯π and π–π interactions.

CCDC reference: 1433130

1. Chemical context

The synthesis and functionalization of indoles has been a major area of focus for researchers for several decades. Indoles are of great importance in view of their natural occurrence as a prominent sub-structure of a large number of alkaloids (Somei & Yamada, 2003 ; Hibino & Choshi, 2002 ) and wide-ranging biological activities (Gribble, 1995 ). They also constitute an important moiety of various drugs. In addition, 1,2,4-triazoles are an important class of heterocyclic compounds which are well known for their potential antimicrobial properties. Substituted 1,2,4-triazoles are associated with diverse biological activities such as fungicidal, antimicrobial, anticonvulsant and antiviral activities (Walser et al., 1991 ; Eweiss et al., 1986 ; Bhat et al., 2001 ; Kitazaki et al., 1996 ; Todoulou et al., 1994 ). The proper design of indoles and triazoles can be used to prepare Schiff bases. The wide spectrum of biological applications of 1,2,4-triazoles prompted us to synthesize Schiff bases derived from triazole and indole derivatives. The formation of the azomethine functional group CH=N is thought to be the main reason for the biological properties of Schiff bases. We have reported a number of metal complexes of Schiff bases, recently, which possess very good antimicrobial properties (Kulkarni et al., 2009a ,b , 2011 ).

2. Structural commentary

The title compound, Fig. 1, exists in a trans conformations with respect to the methene C9=C10 [1.322 (2) Å] and acyclic N2=C11 bonds [1.278 (2) Å]. The triazole ring is almost planar [maximum deviation of 0.011 (2) Å for atom C13], as is the indole ring [maximum deviation of 0.031 (2) Å for atom C4]. The triazole ring is almost normal to both the indole and benzene rings with dihedral angles of 88.66 (9) and 84.51 (10)°, respectively, while the indole and benzene ring are inclined to one another by 61.25 (8)°. The bond lengths and angles in the triazole-thione moiety of the title molecule are comparable to those reported for related compounds (Fun et al., 2008 ; Goh et al., 2009 ; Asad et al., 2010 ).

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

3. Supramolecular features

In the crystal, molecules are linked via pairs of N4—H4B⋯S1 hydrogen bonds, forming inversion dimers with an $[R_{2}^{2}]$ (8)ring motif (Table 1 and Fig. 2). The dimers are linked by C—H⋯π interactions (Table 1), forming chains along [1 $[\overline{1}]$ 0]. The chains are linked by slipped parallel π–·π interactions involving inversion-related triazole rings [Cg2⋯Cg2ⁱ = 3.4339 (13) Å; Cg2 is the centroid of the triazole ring (N3–N5/C12/C13); interplanar distance = 3.3696 (8) Å, slippage = 0.662 Å; symmetry code: (i) −x, −y + 1, −z + 2], forming layers parallel to the ab plane.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C18–C23 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯S1ⁱ	0.91 (2)	2.35 (2)	3.257 (2)	177.1 (15)
C4—H4A⋯Cg1ⁱⁱ	0.93	2.93	3.724 (2)	144
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x, -y, -z+2.

Figure 2
The crystal packing of the title compound viewed along the a axis. The N—H⋯S hydrogen bonds are shown as dashed lines (see Table 1

). H atoms not involved in hydrogen bonding have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 35.6, last update May 2015; Groom and Allen, 2014 ) revealed the presence of 60 structures containing the triazole-thione moiety but only four structures containing the fluvastatin [systematic name: (3R,5S,6E)-7-[3-(4-fluorophenyl)-1-(propan-2-yl)-1H-indol-2-yl]-3,5-dihydroxyhept-6-enoic acid] nucleus. These include 5-[3-(4-fluorophenyl)-1-isopropyl-1H-indol-2-yl]-1-(X)penta-2,4-diene-1-one (Kalalbandi et al., 2015 ), where X = 4-nitrophenyl (NUHNAH), 2-hydroxyphenyl (NUHNEL), 4-methoxyphenyl (NUHNIP) and 4-chlorophenyl (NUHNOV). In the four compounds, the 4-fluorophenyl ring of the fluvastatin nucleus is inclined to the indole ring by dihedral angles ranging from ca 46.66 to 68.59°, compared to 61.25 (8)° for the title compound.

5. Synthesis and crystallization

The title compound was synthesized following a reported procedure (Kulkarni et al., 2011). A hot ethanolic solution (60 ml) of 3-substituted-4-amino-5-mercapto-1,2,4-triazole (0.01 mol) and fluvastatin (0.01 mol) were refluxed for 4–5 h with addition of 4–5 drops of concentrated hydrochloric acid. The precipitate obtained after evaporation of the solvent was filtered and washed with cold ethanol and recrystallized from hot ethanol. Crystals suitable for single-crystal diffraction analysis were obtained by slow evaporation of a solution in chloroform (yield: 76%; m.p.: 469 K). ¹H NMR (d₆-DMSO): 10.6 (s, 1H, NH), 10.04 (s, 1H, CH=N), 7.1–7.6 (m, 8H, Ar–H), 6.47–6.56 (d, 2H, –CH=CH–), 2.38 (s, 1H, –CH₃), 6.47–6.56 (s, 6H, isopropyl group). IR (KBr) cm⁻¹: 3220, 3180 (N—H), 2753 (C—H), 1619 (C=N), 1500–1600 47 (C=C), 1102 (C=S). FAB MS: m/z 419. Elemental analysis: observed (calculated for C₂₃H₂₂FN₅S) C, 65.94 (65.87); H, 5.19 (5.25); N, 16.66 (16.71) %.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N-bound H atom was located in a difference Fourier map and freely refined. The C-bound H atoms were positioned geometrically [C—H = 0.93–0.98 Å] and refined using a riding model with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₃H₂₂FN₅S
M_r	419.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	297
a, b, c (Å)	6.4388 (8), 23.482 (3), 14.572 (3)
β (°)	100.5009 (19)
V (Å³)	2166.3 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.18
Crystal size (mm)	0.40 × 0.27 × 0.09

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.779, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	24228, 5094, 3393
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.04
No. of reflections	5094
No. of parameters	278
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1433130

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015020101/su5226sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015020101/su5226Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015020101/su5226Isup3.cml

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXL2013 (Sheldrick, 2015) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) and PLATON (Spek, 2009).

4-({(1E,2E)-3-[3-(4-Fluorophenyl)-1-isopropyl-1H-indol-2-yl]allylidene}amino)-5-methyl-1H-1,2,4-triazole-5(4H)-thione top

Crystal data top

C₂₃H₂₂FN₅S	F(000) = 880
M_r = 419.51	D_x = 1.286 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.4388 (8) Å	Cell parameters from 5835 reflections
b = 23.482 (3) Å	θ = 2.8–27.5°
c = 14.572 (3) Å	µ = 0.18 mm⁻¹
β = 100.5009 (19)°	T = 297 K
V = 2166.3 (6) Å³	Block, yellow
Z = 4	0.40 × 0.27 × 0.09 mm

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	5094 independent reflections
Radiation source: fine-focus sealed tube	3393 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 27.8°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.779, T_max = 0.932	k = −30→30
24228 measured reflections	l = −19→18

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)] = 0.046	Hydrogen site location: mixed
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0559P)² + 0.3794P] where P = (F_o² + 2F_c²)/3
5094 reflections	(Δ/σ)_max = 0.001
278 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
S1	0.39854 (8)	0.40778 (2)	0.98203 (4)	0.06099 (17)
F1	0.5717 (2)	0.13276 (6)	1.27264 (9)	0.0912 (4)
N1	−0.3776 (2)	0.17803 (6)	0.86118 (10)	0.0523 (4)
N2	0.0328 (2)	0.36814 (6)	1.09831 (11)	0.0512 (4)
N3	0.0953 (2)	0.42497 (6)	1.09021 (10)	0.0464 (3)
N4	0.2694 (3)	0.49906 (7)	1.07257 (11)	0.0540 (4)
H4B	0.358 (3)	0.5255 (9)	1.0558 (15)	0.073 (7)*
N5	0.1315 (3)	0.51498 (7)	1.13047 (11)	0.0564 (4)
C1	−0.4000 (3)	0.12025 (8)	0.87117 (12)	0.0497 (4)
C2	−0.5378 (3)	0.08101 (9)	0.81951 (14)	0.0598 (5)
H2A	−0.6413	0.0929	0.7702	0.072*
C3	−0.5163 (3)	0.02485 (9)	0.84345 (15)	0.0655 (6)
H3A	−0.6061	−0.0017	0.8093	0.079*
C4	−0.3635 (3)	0.00615 (9)	0.91768 (15)	0.0636 (5)
H4A	−0.3509	−0.0325	0.9313	0.076*
C5	−0.2315 (3)	0.04425 (8)	0.97074 (14)	0.0547 (5)
H5A	−0.1318	0.0318	1.0211	0.066*
C6	−0.2489 (3)	0.10201 (7)	0.94809 (12)	0.0457 (4)
C7	−0.1334 (3)	0.15099 (7)	0.98611 (11)	0.0446 (4)
C8	−0.2146 (3)	0.19687 (8)	0.93150 (12)	0.0474 (4)
C9	−0.1544 (3)	0.25633 (8)	0.93989 (13)	0.0529 (4)
H9A	−0.1696	0.2772	0.8848	0.063*
C10	−0.0801 (3)	0.28383 (8)	1.01813 (13)	0.0503 (4)
H10A	−0.0641	0.2640	1.0743	0.060*
C11	−0.0232 (3)	0.34278 (8)	1.02010 (13)	0.0498 (4)
H11A	−0.0270	0.3626	0.9646	0.060*
C12	0.2548 (3)	0.44453 (8)	1.04702 (12)	0.0478 (4)
C13	0.0300 (3)	0.46845 (8)	1.14103 (13)	0.0507 (4)
C14	−0.1374 (3)	0.46154 (10)	1.19744 (16)	0.0702 (6)
H14A	−0.2661	0.4498	1.1578	0.105*
H14B	−0.1598	0.4971	1.2265	0.105*
H14C	−0.0951	0.4332	1.2446	0.105*
C15	−0.4963 (3)	0.21375 (9)	0.78577 (13)	0.0592 (5)
H15A	−0.4358	0.2520	0.7967	0.071*
C16	−0.7234 (4)	0.22020 (12)	0.79263 (17)	0.0881 (8)
H16A	−0.7933	0.2432	0.7418	0.132*
H16B	−0.7342	0.2382	0.8508	0.132*
H16C	−0.7888	0.1833	0.7897	0.132*
C17	−0.4518 (4)	0.19635 (11)	0.69253 (15)	0.0850 (7)
H17A	−0.5220	0.2219	0.6456	0.127*
H17B	−0.5024	0.1583	0.6785	0.127*
H17C	−0.3023	0.1976	0.6937	0.127*
C18	0.0509 (3)	0.14878 (7)	1.06333 (12)	0.0446 (4)
C19	0.0324 (3)	0.12700 (8)	1.15036 (13)	0.0536 (5)
H19A	−0.0996	0.1158	1.1611	0.064*
C20	0.2057 (3)	0.12172 (9)	1.22087 (14)	0.0604 (5)
H20A	0.1915	0.1075	1.2789	0.072*
C21	0.3980 (3)	0.13781 (9)	1.20369 (14)	0.0602 (5)
C22	0.4252 (3)	0.15878 (9)	1.11945 (15)	0.0624 (5)
H22A	0.5585	0.1693	1.1094	0.075*
C23	0.2508 (3)	0.16406 (8)	1.04971 (13)	0.0548 (5)
H23A	0.2676	0.1783	0.9919	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0679 (3)	0.0568 (3)	0.0619 (3)	−0.0073 (2)	0.0215 (3)	−0.0065 (2)
F1	0.0731 (8)	0.1057 (11)	0.0794 (9)	0.0101 (7)	−0.0271 (7)	0.0028 (8)
N1	0.0596 (9)	0.0492 (9)	0.0423 (8)	0.0011 (7)	−0.0065 (7)	0.0004 (7)
N2	0.0588 (9)	0.0437 (8)	0.0510 (9)	−0.0046 (7)	0.0099 (7)	−0.0012 (7)
N3	0.0505 (8)	0.0427 (8)	0.0439 (8)	−0.0035 (6)	0.0032 (7)	−0.0005 (6)
N4	0.0575 (9)	0.0487 (9)	0.0558 (10)	−0.0077 (8)	0.0106 (8)	−0.0006 (7)
N5	0.0577 (9)	0.0509 (9)	0.0594 (10)	−0.0023 (8)	0.0073 (8)	−0.0055 (8)
C1	0.0537 (10)	0.0520 (11)	0.0423 (10)	−0.0005 (8)	0.0059 (8)	−0.0043 (8)
C2	0.0636 (12)	0.0635 (13)	0.0485 (11)	−0.0081 (10)	0.0005 (9)	−0.0069 (9)
C3	0.0713 (13)	0.0632 (13)	0.0612 (13)	−0.0189 (11)	0.0100 (11)	−0.0146 (10)
C4	0.0787 (14)	0.0463 (11)	0.0681 (13)	−0.0077 (10)	0.0197 (12)	−0.0062 (10)
C5	0.0589 (11)	0.0493 (11)	0.0564 (11)	0.0029 (9)	0.0121 (9)	0.0011 (9)
C6	0.0490 (10)	0.0459 (10)	0.0424 (9)	0.0021 (8)	0.0091 (8)	−0.0026 (8)
C7	0.0495 (10)	0.0432 (9)	0.0402 (9)	0.0031 (8)	0.0061 (8)	−0.0008 (7)
C8	0.0523 (10)	0.0471 (10)	0.0407 (9)	0.0010 (8)	0.0023 (8)	−0.0023 (8)
C9	0.0603 (11)	0.0470 (10)	0.0474 (10)	0.0030 (8)	−0.0005 (9)	0.0053 (8)
C10	0.0557 (10)	0.0455 (10)	0.0495 (10)	0.0001 (8)	0.0091 (8)	0.0010 (8)
C11	0.0499 (10)	0.0483 (10)	0.0494 (11)	−0.0007 (8)	0.0040 (8)	0.0022 (8)
C12	0.0503 (10)	0.0486 (10)	0.0416 (9)	−0.0048 (8)	0.0007 (8)	0.0028 (8)
C13	0.0515 (10)	0.0502 (11)	0.0481 (10)	0.0006 (8)	0.0029 (8)	−0.0056 (8)
C14	0.0722 (13)	0.0654 (13)	0.0783 (15)	−0.0021 (11)	0.0277 (12)	−0.0120 (11)
C15	0.0663 (12)	0.0599 (12)	0.0457 (11)	0.0063 (10)	−0.0046 (9)	0.0045 (9)
C16	0.0896 (17)	0.0990 (19)	0.0737 (15)	0.0358 (15)	0.0092 (13)	0.0178 (14)
C17	0.1087 (19)	0.0920 (18)	0.0548 (13)	0.0203 (15)	0.0165 (13)	0.0172 (12)
C18	0.0495 (10)	0.0391 (9)	0.0436 (9)	0.0042 (7)	0.0041 (8)	−0.0019 (7)
C19	0.0544 (10)	0.0573 (11)	0.0481 (10)	0.0006 (9)	0.0064 (8)	0.0038 (9)
C20	0.0727 (13)	0.0614 (12)	0.0437 (10)	0.0064 (10)	0.0016 (9)	0.0065 (9)
C21	0.0584 (12)	0.0567 (12)	0.0572 (12)	0.0080 (9)	−0.0111 (9)	−0.0031 (10)
C22	0.0464 (10)	0.0647 (13)	0.0736 (14)	0.0022 (9)	0.0042 (10)	−0.0006 (11)
C23	0.0555 (11)	0.0580 (11)	0.0508 (11)	0.0036 (9)	0.0094 (9)	0.0054 (9)

Geometric parameters (Å, º) top

S1—C12	1.6785 (19)	C9—H9A	0.9300
F1—C21	1.365 (2)	C10—C11	1.431 (3)
N1—C1	1.375 (2)	C10—H10A	0.9300
N1—C8	1.398 (2)	C11—H11A	0.9300
N1—C15	1.480 (2)	C13—C14	1.479 (3)
N2—C11	1.278 (2)	C14—H14A	0.9600
N2—N3	1.405 (2)	C14—H14B	0.9600
N3—C13	1.372 (2)	C14—H14C	0.9600
N3—C12	1.377 (2)	C15—C16	1.491 (3)
N4—C12	1.332 (2)	C15—C17	1.496 (3)
N4—N5	1.383 (2)	C15—H15A	0.9800
N4—H4B	0.91 (2)	C16—H16A	0.9600
N5—C13	1.297 (2)	C16—H16B	0.9600
C1—C2	1.400 (3)	C16—H16C	0.9600
C1—C6	1.410 (2)	C17—H17A	0.9600
C2—C3	1.365 (3)	C17—H17B	0.9600
C2—H2A	0.9300	C17—H17C	0.9600
C3—C4	1.394 (3)	C18—C23	1.385 (2)
C3—H3A	0.9300	C18—C19	1.393 (2)
C4—C5	1.371 (3)	C19—C20	1.377 (3)
C4—H4A	0.9300	C19—H19A	0.9300
C5—C6	1.396 (3)	C20—C21	1.361 (3)
C5—H5A	0.9300	C20—H20A	0.9300
C6—C7	1.426 (2)	C21—C22	1.363 (3)
C7—C8	1.384 (2)	C22—C23	1.376 (3)
C7—C18	1.480 (2)	C22—H22A	0.9300
C8—C9	1.448 (3)	C23—H23A	0.9300
C9—C10	1.322 (2)

C1—N1—C8	108.31 (14)	N3—C12—S1	128.32 (14)
C1—N1—C15	126.00 (15)	N5—C13—N3	110.63 (16)
C8—N1—C15	125.60 (16)	N5—C13—C14	126.34 (17)
C11—N2—N3	113.96 (15)	N3—C13—C14	123.02 (17)
C13—N3—C12	109.04 (15)	C13—C14—H14A	109.5
C13—N3—N2	122.74 (14)	C13—C14—H14B	109.5
C12—N3—N2	127.16 (15)	H14A—C14—H14B	109.5
C12—N4—N5	114.22 (16)	C13—C14—H14C	109.5
C12—N4—H4B	126.7 (14)	H14A—C14—H14C	109.5
N5—N4—H4B	119.1 (14)	H14B—C14—H14C	109.5
C13—N5—N4	103.77 (15)	N1—C15—C16	112.83 (18)
N1—C1—C2	131.40 (17)	N1—C15—C17	111.16 (17)
N1—C1—C6	108.25 (15)	C16—C15—C17	116.2 (2)
C2—C1—C6	120.35 (18)	N1—C15—H15A	105.2
C3—C2—C1	118.28 (19)	C16—C15—H15A	105.2
C3—C2—H2A	120.9	C17—C15—H15A	105.2
C1—C2—H2A	120.9	C15—C16—H16A	109.5
C2—C3—C4	121.82 (19)	C15—C16—H16B	109.5
C2—C3—H3A	119.1	H16A—C16—H16B	109.5
C4—C3—H3A	119.1	C15—C16—H16C	109.5
C5—C4—C3	120.6 (2)	H16A—C16—H16C	109.5
C5—C4—H4A	119.7	H16B—C16—H16C	109.5
C3—C4—H4A	119.7	C15—C17—H17A	109.5
C4—C5—C6	119.07 (19)	C15—C17—H17B	109.5
C4—C5—H5A	120.5	H17A—C17—H17B	109.5
C6—C5—H5A	120.5	C15—C17—H17C	109.5
C5—C6—C1	119.82 (17)	H17A—C17—H17C	109.5
C5—C6—C7	132.71 (17)	H17B—C17—H17C	109.5
C1—C6—C7	107.42 (15)	C23—C18—C19	117.50 (17)
C8—C7—C6	106.79 (15)	C23—C18—C7	121.29 (16)
C8—C7—C18	129.11 (16)	C19—C18—C7	121.02 (16)
C6—C7—C18	123.81 (15)	C20—C19—C18	121.35 (18)
C7—C8—N1	109.23 (15)	C20—C19—H19A	119.3
C7—C8—C9	129.40 (16)	C18—C19—H19A	119.3
N1—C8—C9	121.36 (16)	C21—C20—C19	118.57 (18)
C10—C9—C8	126.37 (17)	C21—C20—H20A	120.7
C10—C9—H9A	116.8	C19—C20—H20A	120.7
C8—C9—H9A	116.8	C20—C21—C22	122.43 (18)
C9—C10—C11	122.75 (17)	C20—C21—F1	119.42 (19)
C9—C10—H10A	118.6	C22—C21—F1	118.15 (19)
C11—C10—H10A	118.6	C21—C22—C23	118.45 (19)
N2—C11—C10	119.87 (17)	C21—C22—H22A	120.8
N2—C11—H11A	120.1	C23—C22—H22A	120.8
C10—C11—H11A	120.1	C22—C23—C18	121.70 (18)
N4—C12—N3	102.30 (15)	C22—C23—H23A	119.2
N4—C12—S1	129.35 (14)	C18—C23—H23A	119.2

C11—N2—N3—C13	135.05 (17)	N3—N2—C11—C10	176.73 (15)
C11—N2—N3—C12	−58.1 (2)	C9—C10—C11—N2	174.77 (18)
C12—N4—N5—C13	0.3 (2)	N5—N4—C12—N3	1.0 (2)
C8—N1—C1—C2	−179.70 (19)	N5—N4—C12—S1	−177.04 (13)
C15—N1—C1—C2	−3.0 (3)	C13—N3—C12—N4	−1.95 (18)
C8—N1—C1—C6	−0.5 (2)	N2—N3—C12—N4	−170.26 (15)
C15—N1—C1—C6	176.20 (16)	C13—N3—C12—S1	176.15 (14)
N1—C1—C2—C3	176.7 (2)	N2—N3—C12—S1	7.8 (2)
C6—C1—C2—C3	−2.4 (3)	N4—N5—C13—N3	−1.6 (2)
C1—C2—C3—C4	0.6 (3)	N4—N5—C13—C14	179.73 (18)
C2—C3—C4—C5	1.4 (3)	C12—N3—C13—N5	2.3 (2)
C3—C4—C5—C6	−1.5 (3)	N2—N3—C13—N5	171.27 (15)
C4—C5—C6—C1	−0.4 (3)	C12—N3—C13—C14	−178.93 (17)
C4—C5—C6—C7	−177.33 (19)	N2—N3—C13—C14	−10.0 (3)
N1—C1—C6—C5	−176.99 (16)	C1—N1—C15—C16	69.7 (3)
C2—C1—C6—C5	2.3 (3)	C8—N1—C15—C16	−114.2 (2)
N1—C1—C6—C7	0.7 (2)	C1—N1—C15—C17	−62.8 (3)
C2—C1—C6—C7	−179.99 (17)	C8—N1—C15—C17	113.3 (2)
C5—C6—C7—C8	176.61 (19)	C8—C7—C18—C23	−58.3 (3)
C1—C6—C7—C8	−0.63 (19)	C6—C7—C18—C23	114.7 (2)
C5—C6—C7—C18	2.3 (3)	C8—C7—C18—C19	126.8 (2)
C1—C6—C7—C18	−174.99 (15)	C6—C7—C18—C19	−60.2 (2)
C6—C7—C8—N1	0.35 (19)	C23—C18—C19—C20	1.1 (3)
C18—C7—C8—N1	174.31 (16)	C7—C18—C19—C20	176.15 (17)
C6—C7—C8—C9	179.80 (18)	C18—C19—C20—C21	−0.6 (3)
C18—C7—C8—C9	−6.2 (3)	C19—C20—C21—C22	−0.1 (3)
C1—N1—C8—C7	0.1 (2)	C19—C20—C21—F1	−179.84 (17)
C15—N1—C8—C7	−176.62 (17)	C20—C21—C22—C23	0.4 (3)
C1—N1—C8—C9	−179.43 (17)	F1—C21—C22—C23	−179.90 (18)
C15—N1—C8—C9	3.9 (3)	C21—C22—C23—C18	0.1 (3)
C7—C8—C9—C10	−31.3 (3)	C19—C18—C23—C22	−0.8 (3)
N1—C8—C9—C10	148.07 (19)	C7—C18—C23—C22	−175.87 (17)
C8—C9—C10—C11	179.64 (17)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C18–C23 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···S1ⁱ	0.91 (2)	2.35 (2)	3.257 (2)	177.1 (15)
C4—H4A···Cg1ⁱⁱ	0.93	2.93	3.724 (2)	144

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

Acknowledgements

This research was supported by a PRGS Research Grant (No. RDU 130803).

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