(2Z)-2-(5-Fluoro-1-methyl-2-oxoindolin-3-yl­idene)-N-(3-fluoro­phen­yl)hydrazine-1-carbo­thio­amide

Atioğlu, Z.; Sevinçli, Z. Ş.; Karalı, N.; Akkurt, M.; Ersanlı, C.C.

doi:10.1107/S2414314617009002

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170900

https://doi.org/10.1107/S2414314617009002

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(2Z)-2-(5-Fluoro-1-methyl-2-oxoindolin-3-ylidene)-N-(3-fluorophenyl)hydrazine-1-carbothioamide

Zeliha Atioğlu,^a ^* Zekiye Şeyma Sevinçli,^b Nilgün Karalı,^c Mehmet Akkurt ^d and Cem Cüneyt Ersanlı ^e

^aİlke Education and Health Foundation, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Yüzüncü Yıl University, 65080 Tuşba, Van, Turkey, ^cDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Ístanbul University, 34116 Beyazıt–Ístanbul, Turkey, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^eDepartment of Physics, Faculty of Arts and Sciences, Sinop University, 57010 Sinop, Turkey
^*Correspondence e-mail: zeliha.atioglu@kapadokya.edu.tr

Edited by J. Simpson, University of Otago, New Zealand (Received 11 June 2017; accepted 16 June 2017; online 20 June 2017)

In the title compound, C₁₆H₁₂F₂N₄OS, the whole molecule is essentially planar (r.m.s deviation = 0.003 Å), with only the H atoms of the methyl group lying out of the molecular plane. A planar indole fused-ring system (r.m.s deviation = 0.004 Å) is linked through a hydrazine–carbothioamide bridge to a fluorobenzene ring, with the indole ring system and inclined to the fluorobenzene ring by 4.26 (14)°. The planarity of the molecule is strengthened by three intramolecular N—H⋯N, N—H⋯O and C—H⋯S hydrogen bonds that generate S(5), S(6) and S(6) ring motifs, respectively. In the crystal, π–π stacking interactions combine with C—H⋯·F hydrogen bonds to link the molecules into layers parallel to the (10-1) plane.

Keywords: crystal structure; 2,3-dihydro-1H-indene; fluorobenzene; intramolecular hydrogen bonds; π–π stacking interactions; synthesis.

CCDC reference: 1556401

Structure description

The indole heterocyclic ring system is a significant component of many pharmaceutical agents, including compounds with antiviral, anti-inflammatory and antineoplastic properties (Ma et al., 2015 ). Halogenated and N-alkylated isatin derivatives demonstrate antitumour activity (Karalı et al., 2007 ; Podichetty et al., 2009 ). Thiosemicarbazone compounds that incorporate isatin units also have various types of biological effects, including antiviral, antibacterial and antitumour activity (Thanh et al., 2016 ). Isatin 3-thiosemicarbazones, which show anti-HIV effects, are also used in the treatment of smallpox and vaccinia viruses, and of other groups of viruses, including adenovirus and herpesvirus (Bal et al., 2005 ; Hall et al., 2009 ; Thanh et al., 2016). Finally, isatin [N⁴-(phenyl substituted)thiosemicarbazone] derivatives have been shown to be significantly more selective and effective against multidrug resistance when compared to the activity of N⁴-alkyl and N⁴-cycloalkylthiosemicarbazones (Hall et al., 2009, 2011 ).

As shown in Fig. 1, the molecule of the title compound is essentially planar (r.m.s deviation = 0.003 Å), with only the H atoms of the C9 methyl group protruding from the molecular plane. The almost planar indole fused-ring (N1/C1–C8) (r.m.s deviation deviation = 0.004 Å) makes a dihedral angle of 4.26 (14)° with the C11–C16 benzene ring. The N2—N3—C10=S1 and N2—N3—C10—N4 torsion angles are 172.6 (2) and −6.1 (4)°, respectively, again in keeping with the planarity of the molecule. Three intramolecular N—H⋯N, N—H⋯O and C—H⋯S hydrogen bonds (Table 1) generate S(5), S(6) and S(6) ring motifs, respectively, and also contribute significantly to the molecular planarity.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1	0.88 (3)	2.08 (3)	2.761 (3)	134 (2)
N4—H4N⋯N2	0.87 (3)	2.07 (3)	2.579 (3)	117 (3)
C2—H2⋯F2ⁱ	0.93	2.44	3.370 (5)	176
C12—H12⋯S1	0.93	2.60	3.251 (3)	127
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

All bond lengths and angles are within normal ranges and are in agreement with those reported for the related compounds 2-(5-fluoro-1-methyl-2-oxoindolin-3-ylidene)-N-[4-(methylsulfanyl)phenyl]hydrazine-1-carbothioamide (Atioğlu et al., 2017 ), (3E)-3-[(4-butylphenyl)imino]-1,3-dihydro-2H-indol-2-one (Akkurt et al., 2003 ), N′-[(2Z)-3-allyl-4-oxo-1,3-thiazolidin-2-ylidene]-5-fluoro-3-phenyl-1H-indole-2-carbohydrazide (Akkurt et al., 2009 ), 2-(4-isobutylphenyl)-N′-[(3Z)-2-oxoindolin-3-ylidene]propanohydrazide (Mohamed et al., 2012 ) and series of 5-fluoro-1H-indole-2,3-dione 3-thiosemicarbazone (Özbey et al., 2006 ) and 5-trifluoromethoxy-1H-indole-2,3-dione 3-thiosemicarbazone derivatives (Kaynak et al., 2013 ).

In the crystal structure of the title compound, C2—H⋯F2 hydrogen bonds link molecules into zigzag C(14) chains along b. π–π stacking interactions between the oxopyrrole and benzene rings [Cg1⋯Cg3ⁱⁱⁱ = 3.818 (2) Å; symmetry code: (iii) 1 − x, 1 − y, 1 − z; Cg1 and Cg3 are the centroids of the N1/C1–C8 and C11–C16 rings, respectively] (Table 1) link these chains into layers parallel to the (10 $[\overline{1}]$ ) plane (Fig. 2).

Figure 2
The layers of molecules of the title compound, viewed along the a-axis direction.

Synthesis and crystallization

Steps in the synthesis of the title compound (5) are shown in Fig. 3.

Figure 3
The synthesis of the title compound.

(i) N-(3-Fluorophenyl)thiosemicarbazide (2)

To a solution of hydrazine hydrate (5 mmol) in ethanol (10 ml), a suspension of 3-fluorophenyl isothiocyanate, 1 (5 mmol), in ethanol (10 ml) was added dropwise with vigorous stirring and cooling in an ice bath. The mixture was allowed to stand overnight. The crystals formed were recrystallized from ethanol solution.

(ii) 5-Fluoro-1-methyl-1H-indole-2,3-dione (4)

A suspension of 5-fluoro-1H-indole-2,3-dione, 3 (5 mmol), K₂CO₃ (7 mmol) and KI (1 mmol) in anhydrous DMF (5 ml) was stirred for 30 min at room temperature. After addition of iodomethane (15 mmol), the mixture was refluxed for 4 h. The product was poured onto ice–water and filtered.

(iii) (2Z)-2-(5-Fluoro-1-methyl-2-oxoindolin-1-ylidene)-N-(3-fluorophenyl)hydrazine-1-carbothioamide (5)

A solution of N-(3-fluorophenyl)thiosemicarbazide, 2 (2.5 mmol), in ethanol (10 ml) was added to a solution of 5-fluoro-1-methyl-1H-indole-2,3-dione, 4 (2.5 mmol), in ethanol (20 ml). The mixture was refluxed on a water bath for 8 h. The product formed after cooling was filtered off and washed with ethanol or recrystallized from ethanol. Orange crystals were obtained (82% yield; m.p. 510–516 K).

IR (KBr): ν 3288, 3226 (NH), 1695 (C=O), 1276 (C=S); ¹H NMR (DMSO-d₆, 400 MHz): δ 3.20 (s, 3H, ind. N—CH₃), 7.09–7.16 (m, 2H, ind. C₇—H, fen. C₄—H), 7.28 (dt, J = 9.00, 2.70 Hz, 1H, ind. C₆—H), 7.43–7.51 (m, 2H, fen. C_5,6—H), 7.59–7.65 (m, 2H, ind. C₄—H, fen. C₂—H), 10.86 (s, 1H, N₄—H), 12.62 (s, 1H, N₂—H). Analysis calculated for C₁₆H₁₂F₂N₄OS: C 55.48, H 3.49, N 16.18%; found: C 55.26, H 3.41, N 16.18%.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₂F₂N₄OS
M_r	346.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.2648 (8), 25.571 (2), 7.6662 (6)
β (°)	108.248 (3)
V (Å³)	1538.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.18 × 0.16 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.664, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	33521, 3145, 2536
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.125, 1.20
No. of reflections	3145
No. of parameters	227
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ), WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1556401

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617009002/sj4121sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009002/sj4121Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617009002/sj4121Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

(2Z)-2-(5-Fluoro-1-methyl-2-oxoindolin-3-ylidene)-N-(3-fluorophenyl)hydrazine-1-carbothioamide top

Crystal data top

C₁₆H₁₂F₂N₄OS	F(000) = 712
M_r = 346.36	D_x = 1.495 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2648 (8) Å	Cell parameters from 9857 reflections
b = 25.571 (2) Å	θ = 3.1–26.4°
c = 7.6662 (6) Å	µ = 0.24 mm⁻¹
β = 108.248 (3)°	T = 296 K
V = 1538.7 (2) Å³	Block, orange
Z = 4	0.18 × 0.16 × 0.15 mm

Data collection top

Bruker APEX-II CCD diffractometer	2536 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.061
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θ_max = 26.5°, θ_min = 2.9°
T_min = 0.664, T_max = 0.745	h = −10→10
33521 measured reflections	k = −31→32
3145 independent reflections	l = −8→9

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.062	w = 1/[σ²(F_o²) + (0.016P)² + 1.7256P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.125	(Δ/σ)_max = 0.001
S = 1.20	Δρ_max = 0.20 e Å⁻³
3145 reflections	Δρ_min = −0.22 e Å⁻³
227 parameters	Extinction correction: Shelxl-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0148 (18)

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
C1	0.3755 (4)	0.68818 (11)	0.1055 (4)	0.0491 (8)
C2	0.3839 (6)	0.74228 (13)	0.1121 (6)	0.0656 (10)
H2	0.2990	0.7627	0.0334	0.079*
C3	0.5238 (6)	0.76481 (13)	0.2405 (6)	0.0737 (12)
H3	0.5339	0.8010	0.2482	0.088*
C4	0.6471 (5)	0.73406 (14)	0.3560 (6)	0.0671 (11)
C5	0.6409 (4)	0.68024 (12)	0.3531 (5)	0.0532 (8)
H5	0.7255	0.6602	0.4339	0.064*
C6	0.5028 (4)	0.65757 (10)	0.2241 (4)	0.0438 (7)
C7	0.4530 (4)	0.60370 (11)	0.1799 (4)	0.0397 (6)
C8	0.2885 (4)	0.60452 (11)	0.0230 (4)	0.0440 (7)
C9	0.0958 (5)	0.67445 (15)	−0.1501 (5)	0.0724 (11)
H9A	0.0309	0.6450	−0.2121	0.109*
H9B	0.1258	0.6961	−0.2376	0.109*
H9C	0.0289	0.6944	−0.0916	0.109*
C10	0.5401 (3)	0.47150 (10)	0.3010 (4)	0.0358 (6)
C11	0.8089 (3)	0.44869 (10)	0.5535 (4)	0.0363 (6)
C12	0.8077 (4)	0.39485 (11)	0.5441 (4)	0.0469 (7)
H12	0.7225	0.3771	0.4553	0.056*
C13	0.9371 (4)	0.36828 (11)	0.6708 (5)	0.0496 (8)
C14	1.0649 (4)	0.39157 (13)	0.8042 (4)	0.0493 (8)
H14	1.1501	0.3721	0.8868	0.059*
C15	1.0629 (4)	0.44527 (13)	0.8118 (4)	0.0521 (8)
H15	1.1480	0.4627	0.9019	0.063*
C16	0.9369 (4)	0.47364 (11)	0.6882 (4)	0.0449 (7)
H16	0.9378	0.5100	0.6954	0.054*
N1	0.2499 (3)	0.65613 (10)	−0.0125 (4)	0.0514 (7)
N2	0.5351 (3)	0.56333 (8)	0.2634 (3)	0.0383 (5)
N3	0.4656 (3)	0.51577 (9)	0.2078 (3)	0.0398 (6)
H3N	0.368 (4)	0.5131 (11)	0.119 (4)	0.041 (8)*
N4	0.6882 (3)	0.48115 (9)	0.4309 (3)	0.0410 (6)
H4N	0.710 (4)	0.5146 (12)	0.441 (4)	0.045 (8)*
O1	0.2066 (3)	0.56682 (8)	−0.0540 (3)	0.0530 (6)
S1	0.43668 (10)	0.41527 (3)	0.24325 (11)	0.0501 (3)
F1	0.7820 (3)	0.75761 (9)	0.4809 (4)	0.0957 (8)
F2	0.9353 (3)	0.31510 (7)	0.6611 (3)	0.0879 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.068 (2)	0.0349 (15)	0.0554 (19)	0.0101 (14)	0.0353 (17)	0.0061 (13)
C2	0.099 (3)	0.0398 (18)	0.076 (2)	0.0161 (19)	0.053 (2)	0.0130 (17)
C3	0.118 (4)	0.0343 (17)	0.093 (3)	−0.007 (2)	0.068 (3)	−0.0037 (19)
C4	0.092 (3)	0.048 (2)	0.080 (3)	−0.023 (2)	0.053 (2)	−0.0183 (19)
C5	0.062 (2)	0.0440 (17)	0.063 (2)	−0.0084 (15)	0.0328 (17)	−0.0069 (15)
C6	0.0556 (18)	0.0321 (14)	0.0517 (17)	0.0035 (13)	0.0284 (15)	0.0015 (13)
C7	0.0459 (16)	0.0342 (14)	0.0434 (16)	0.0050 (12)	0.0205 (13)	0.0022 (12)
C8	0.0466 (17)	0.0416 (16)	0.0480 (17)	0.0089 (13)	0.0210 (14)	0.0060 (13)
C9	0.071 (3)	0.072 (2)	0.071 (2)	0.031 (2)	0.018 (2)	0.025 (2)
C10	0.0374 (15)	0.0358 (14)	0.0336 (14)	0.0046 (11)	0.0102 (11)	−0.0001 (11)
C11	0.0315 (13)	0.0381 (14)	0.0372 (14)	−0.0007 (11)	0.0079 (11)	−0.0003 (11)
C12	0.0385 (15)	0.0377 (15)	0.0534 (18)	0.0001 (12)	−0.0016 (13)	−0.0046 (13)
C13	0.0412 (17)	0.0354 (15)	0.064 (2)	0.0051 (12)	0.0043 (15)	0.0013 (14)
C14	0.0352 (15)	0.0566 (19)	0.0483 (18)	0.0069 (13)	0.0020 (13)	0.0066 (14)
C15	0.0394 (16)	0.0569 (19)	0.0484 (18)	−0.0045 (14)	−0.0030 (14)	−0.0038 (15)
C16	0.0432 (16)	0.0377 (15)	0.0477 (17)	−0.0046 (12)	0.0053 (13)	−0.0008 (12)
N1	0.0571 (16)	0.0451 (14)	0.0540 (16)	0.0174 (12)	0.0206 (13)	0.0116 (12)
N2	0.0425 (13)	0.0308 (11)	0.0417 (13)	0.0027 (10)	0.0135 (10)	−0.0007 (10)
N3	0.0398 (14)	0.0325 (12)	0.0396 (13)	0.0026 (10)	0.0018 (11)	−0.0008 (10)
N4	0.0407 (13)	0.0278 (12)	0.0450 (14)	−0.0004 (10)	−0.0003 (10)	0.0004 (10)
O1	0.0468 (12)	0.0502 (13)	0.0551 (13)	0.0028 (10)	0.0061 (10)	0.0019 (10)
S1	0.0461 (4)	0.0347 (4)	0.0553 (5)	−0.0032 (3)	−0.0047 (3)	0.0001 (3)
F1	0.114 (2)	0.0690 (15)	0.116 (2)	−0.0432 (14)	0.0545 (17)	−0.0386 (14)
F2	0.0730 (14)	0.0385 (11)	0.1170 (19)	0.0134 (10)	−0.0208 (13)	−0.0008 (11)

Geometric parameters (Å, º) top

C1—C2	1.385 (4)	C9—H9C	0.9600
C1—C6	1.395 (4)	C10—N4	1.337 (3)
C1—N1	1.407 (4)	C10—N3	1.377 (3)
C2—C3	1.387 (6)	C10—S1	1.660 (3)
C2—H2	0.9300	C11—C12	1.378 (4)
C3—C4	1.370 (6)	C11—C16	1.381 (4)
C3—H3	0.9300	C11—N4	1.407 (3)
C4—F1	1.361 (4)	C12—C13	1.378 (4)
C4—C5	1.377 (4)	C12—H12	0.9300
C5—C6	1.382 (4)	C13—C14	1.357 (4)
C5—H5	0.9300	C13—F2	1.362 (3)
C6—C7	1.447 (4)	C14—C15	1.375 (4)
C7—N2	1.290 (3)	C14—H14	0.9300
C7—C8	1.507 (4)	C15—C16	1.375 (4)
C8—O1	1.219 (4)	C15—H15	0.9300
C8—N1	1.365 (4)	C16—H16	0.9300
C9—N1	1.454 (4)	N2—N3	1.356 (3)
C9—H9A	0.9600	N3—H3N	0.88 (3)
C9—H9B	0.9600	N4—H4N	0.87 (3)

C2—C1—C6	121.2 (3)	N4—C10—S1	129.3 (2)
C2—C1—N1	128.6 (3)	N3—C10—S1	117.7 (2)
C6—C1—N1	110.3 (2)	C12—C11—C16	119.5 (3)
C1—C2—C3	117.5 (4)	C12—C11—N4	124.2 (2)
C1—C2—H2	121.2	C16—C11—N4	116.3 (2)
C3—C2—H2	121.2	C13—C12—C11	117.6 (3)
C4—C3—C2	120.4 (3)	C13—C12—H12	121.2
C4—C3—H3	119.8	C11—C12—H12	121.2
C2—C3—H3	119.8	C14—C13—F2	118.2 (3)
F1—C4—C3	118.7 (3)	C14—C13—C12	124.4 (3)
F1—C4—C5	118.1 (4)	F2—C13—C12	117.5 (3)
C3—C4—C5	123.2 (4)	C13—C14—C15	117.0 (3)
C4—C5—C6	116.7 (3)	C13—C14—H14	121.5
C4—C5—H5	121.7	C15—C14—H14	121.5
C6—C5—H5	121.7	C14—C15—C16	121.0 (3)
C5—C6—C1	121.1 (3)	C14—C15—H15	119.5
C5—C6—C7	132.6 (3)	C16—C15—H15	119.5
C1—C6—C7	106.3 (3)	C15—C16—C11	120.6 (3)
N2—C7—C6	125.4 (3)	C15—C16—H16	119.7
N2—C7—C8	127.6 (3)	C11—C16—H16	119.7
C6—C7—C8	107.0 (2)	C8—N1—C1	110.8 (3)
O1—C8—N1	127.5 (3)	C8—N1—C9	123.6 (3)
O1—C8—C7	126.9 (3)	C1—N1—C9	125.5 (3)
N1—C8—C7	105.6 (3)	C7—N2—N3	117.2 (2)
N1—C9—H9A	109.5	N2—N3—C10	119.9 (2)
N1—C9—H9B	109.5	N2—N3—H3N	120.5 (19)
H9A—C9—H9B	109.5	C10—N3—H3N	119.4 (19)
N1—C9—H9C	109.5	C10—N4—C11	132.9 (2)
H9A—C9—H9C	109.5	C10—N4—H4N	111 (2)
H9B—C9—H9C	109.5	C11—N4—H4N	116 (2)
N4—C10—N3	113.0 (2)

C6—C1—C2—C3	0.2 (5)	C11—C12—C13—F2	180.0 (3)
N1—C1—C2—C3	−179.0 (3)	F2—C13—C14—C15	−179.5 (3)
C1—C2—C3—C4	−0.4 (5)	C12—C13—C14—C15	0.3 (5)
C2—C3—C4—F1	−179.7 (3)	C13—C14—C15—C16	−0.4 (5)
C2—C3—C4—C5	−0.1 (6)	C14—C15—C16—C11	0.2 (5)
F1—C4—C5—C6	−179.7 (3)	C12—C11—C16—C15	0.3 (5)
C3—C4—C5—C6	0.8 (5)	N4—C11—C16—C15	−178.5 (3)
C4—C5—C6—C1	−0.9 (5)	O1—C8—N1—C1	180.0 (3)
C4—C5—C6—C7	179.9 (3)	C7—C8—N1—C1	0.8 (3)
C2—C1—C6—C5	0.4 (5)	O1—C8—N1—C9	1.9 (5)
N1—C1—C6—C5	179.8 (3)	C7—C8—N1—C9	−177.3 (3)
C2—C1—C6—C7	179.8 (3)	C2—C1—N1—C8	179.3 (3)
N1—C1—C6—C7	−0.8 (3)	C6—C1—N1—C8	0.0 (4)
C5—C6—C7—N2	1.5 (5)	C2—C1—N1—C9	−2.7 (5)
C1—C6—C7—N2	−177.7 (3)	C6—C1—N1—C9	178.0 (3)
C5—C6—C7—C8	−179.5 (3)	C6—C7—N2—N3	177.4 (3)
C1—C6—C7—C8	1.2 (3)	C8—C7—N2—N3	−1.4 (4)
N2—C7—C8—O1	−1.5 (5)	C7—N2—N3—C10	−174.9 (3)
C6—C7—C8—O1	179.6 (3)	N4—C10—N3—N2	−6.1 (4)
N2—C7—C8—N1	177.7 (3)	S1—C10—N3—N2	172.6 (2)
C6—C7—C8—N1	−1.2 (3)	N3—C10—N4—C11	−177.7 (3)
C16—C11—C12—C13	−0.5 (5)	S1—C10—N4—C11	3.7 (5)
N4—C11—C12—C13	178.3 (3)	C12—C11—N4—C10	10.3 (5)
C11—C12—C13—C14	0.2 (5)	C16—C11—N4—C10	−170.9 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is a centroid of the N1/C1/C6–C8 cyclopentene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1	0.88 (3)	2.08 (3)	2.761 (3)	134 (2)
N4—H4N···N2	0.87 (3)	2.07 (3)	2.579 (3)	117 (3)
C2—H2···F2ⁱ	0.93	2.44	3.370 (5)	176
C9—H9A···O1	0.96	2.54	2.921 (4)	104
C12—H12···S1	0.93	2.60	3.251 (3)	127
C10—S1···Cg1ⁱⁱ	1.66 (1)	3.78 (1)	4.467 (3)	103 (1)

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

Acknowledgements

The authors acknowledge the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer.

References

Akkurt, M., Karaca, S., Cihan, G., Çapan, G. & Büyükgüngör, O. (2009). Acta Cryst. E65, o1009–o1010. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Akkurt, M., Öztürk, S., Erçağ, A., Özgür, M. Ü. & Heinemann, F. W. (2003). Acta Cryst. E59, o780–o782. Web of Science CSD CrossRef IUCr Journals Google Scholar
Atioğlu, Z., Sevinçli, Z. Ş., Karalı, N., Akkurt, M. & Ersanlı, C. C. (2017). IUCrData, 2, x170671–x170671. Google Scholar
Bal, T. R., Anand, B., Yogeeswari, P. & Sriram, D. (2005). Bioorg. Med. Chem. Lett. 15, 4451–4455. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hall, M. D., Brimacombe, K. R., Varonka, M. S., Pluchino, K. M., Monda, J. K., Li, J., Walsh, M. J., Boxer, M. B., Warren, T. H., Fales, H. M. & Gottesman, M. M. (2011). J. Med. Chem. 54, 5878–5889. Web of Science CSD CrossRef CAS PubMed Google Scholar
Hall, M. D., Salam, N. K., Hellawell, J. L., Fales, H. M., Kensler, C. B., Ludwig, J. A., Szakacs, G., Hibbs, D. E. & Gottesman, M. M. (2009). J. Med. Chem. 52, 3191–3204. CrossRef PubMed CAS Google Scholar
Karalı, N., Gürsoy, A., Kandemirli, F., Shvets, N., Kaynak, F. B., Özbey, S., Kovalishyn, V. & Dimoglo, A. (2007). Bioorg. Med. Chem. 15, 5888–5904. Web of Science PubMed Google Scholar
Kaynak, F. B., Özbey, S. & Karalı, N. (2013). J. Mol. Struct. 1049, 157–164. Web of Science CSD CrossRef CAS Google Scholar
Ma, J., Bao, G., Wang, L., Li, W., Xu, B., Du, B., Lv, J., Zhai, X. & Gong, P. (2015). Eur. J. Med. Chem. 96, 173–186. Web of Science CrossRef CAS PubMed Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mohamed, S. K., Akkurt, M., Albayati, M. R., Singh, K. & Potgieter, H. (2012). Acta Cryst. E68, o1222–o1223. CSD CrossRef IUCr Journals Google Scholar
Özbey, S., Kaynak, F. B., Eriksson, L., Karali, N. & Gürsoy, A. (2006). Acta Cryst. A62, s174. CrossRef IUCr Journals Google Scholar
Podichetty, A. K., Faust, A., Kopka, K., Wagner, S., Schober, O., Schäfers, M. & Haufe, G. (2009). Bioorg. Med. Chem. 17, 2680–2688. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thanh, N. D., Giang, N. T. K., Quyen, T. H. & Huong, D. T. (2016). Eur. J. Med. Chem. 123, 532–543. CrossRef PubMed Google Scholar

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