2-(5-Fluoro-1-methyl-2-oxoindolin-3-yl­idene)-N-[4-(methyl­sulfan­yl)phen­yl]hydrazine-1-carbo­thio­amide

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

doi:10.1107/S241431461700671X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170671

https://doi.org/10.1107/S241431461700671X

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2-(5-Fluoro-1-methyl-2-oxoindolin-3-ylidene)-N-[4-(methylsulfanyl)phenyl]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 M. Bolte, Goethe-Universität Frankfurt, Germany (Received 18 April 2017; accepted 4 May 2017; online 9 May 2017)

The title molecule, C₁₇H₁₅FN₄OS₂, obtained from 5-fluoro-1-methyl-1H-indol-2,3-dione, and 3-[4-(methylsulfanyl)phenyl]thiosemicarbazide, has an essentially planar conformation (r.m.s deviation for all non-H atoms = 0.116 Å). Intramolecular N—H⋯N and N—H⋯O hydrogen bonds generate S(5) and S(6) ring motifs, respectively. In the crystal, C—H⋯S hydrogen bonds occur between layers of molecules parallel to the (10-1) plane. Face-to-face π–π stacking interactions are also observed.

Keywords: crystal structure; intramolecular hydrogen bonds; π–π stacking interactions; synthesis; 5-fluoro-1H-indole-2,3-dione.

CCDC reference: 1547812

Structure description

The indole ring system is an important structural component in many pharmaceutical agents, including compounds with antiviral, anti-inflammatory and antitumor properties (Ma et al., 2015 ). 1H-Indole-2,3-dione (isatin) has a wide spectrum of biological properties, such as cytotoxic and antineoplastic effects. Isatin derivatives with halogens and N-alkylhaloisatins have been reported to exhibit anticancer activity (Podichetty et al., 2009 ). The biological activities of thiosemicarbazones, such as anticancer, antiviral, antimicrobial etc, have been known for a long time. Isatin 3-thiosemicarbazone derivatives, which have anti-HIV effects, are used as prophylaxes against smallpox and vaccinia viruses (Bal et al., 2005 ; Hall et al., 2009 ). Isatin 3-[N⁴-(phenyl substituted) thiosemicarbazone] derivatives have been shown to be have significantly more multidrug resistant-selective activity than N⁴-alkyl and N⁴-cycloalkyl thiosemicarbazone derivatives (Hall et al., 2009, 2011 ).

In the title compound (Fig. 1), the N—N—C=S and N—N—C(=S)—N torsion angles are 170.0 (3) and −9.6 (6)°, respectively. Intramolecular N—H⋯N and N—H⋯O hydrogen bonds (Table 1) generate S(5) and S(6) ring motifs, respectively (Fig. 2). All bond lengths and angles are within normal ranges and agree with those reported for (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 ), 5-fluoro-1H-indole-2,3-dione 3-thiosemicarbazone derivatives (Özbey et al., 2006 ; Karayel et al., 2015 ) and 5-trifluoromethoxy-1H-indole-2,3-dione 3-thiosemicarbazone derivatives (Kaynak et al., 2013 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1	0.87 (4)	2.09 (5)	2.757 (5)	133 (5)
N4—H4N⋯N2	0.90 (5)	2.14 (5)	2.598 (5)	110 (3)
C3—H3⋯S1ⁱ	0.93	2.84	3.712 (5)	158
C9—H9B⋯S2ⁱⁱ	0.96	2.84	3.652 (7)	142
C12—H12⋯S1	0.93	2.61	3.256 (4)	128
Symmetry codes: (i) x-1, y, z-1; (ii) $[x-1, -y+1, z-{\script{1\over 2}}]$ .

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

Figure 2
A partial view along the c axis of the N—H⋯N, N—H⋯O and C—H⋯S hydrogen bonding (Table 1

) in the crystal packing of the title compound.

In the crystal, C—H⋯S hydrogen bonds (Table 1) occur between layers of molecules located parallel to the (10 $[\overline{1}]$ ) plane (Fig. 3). Face-to-face π–π stacking interactions [Cg1⋯Cg3(x, 1 − y, − $[{1\over 2}]$ + z) = 3.615 (3) Å and Cg2⋯Cg3(−1 + x, 1 − y, − $[{1\over 2}]$ + z) = 3.835 (3) Å, where Cg1, Cg2 and Cg3 are the centroids of the N1/C1/C6–C8, C1–C6 and C11–C16 rings, respectively] are also observed.

Figure 3
A view along the b axis of the crystal packing of the title compound.

Synthesis and crystallization

Steps in the synthesis of the title compound (5) are shown in Fig. 4.

Figure 4
The synthesis of the title compound 5.

3-[4-(Methylsulfanyl)phenyl]thiosemicarbazide (2)

To a solution of hydrazine hydrate (5 mmol) in ethanol (10 ml), a suspension of 4-(methylsulfanyl)phenylisothiocyanate (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.

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 then filtered.

5-Fluoro-1-methyl-1H-indole-2,3-dione 3-[4-(methylsulfanyl)phenyl] thiosemicarbazone (5)

A solution of N-[(4-methylsulfanyl)phenyl]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 10 h. The product formed after cooling was filtered and washed with ethanol or recrystallized from ethanol. Orange crystals were obtained in 94% yield, m.p. 508–511 K.

IR (KBr): ν 3269, 3226 (NH), 1681 (C=O), 1274 (C=S); ¹H NMR (DMSO-d₆; 400 MHz): δ 2.49 (s, 3H, SCH₃), 3.21 (s, 3H, ind. N—CH₃), 7.15 (dd, J = 8.60, 4.00 Hz, 1H, ind. C7—H), 7.26–7.32 (m, 1H, ind. C6—H), 7.30 (d, J = 8.60 Hz, 2H, fen. C3,5-H), 7.55 (d, J = 8.60 Hz, 2H, fen. C2,6-H), 7.64 (dd, J = 8.00, 2.66 Hz, 1H, ind. C4—H), 10.81 (s, 1H, N4—H), 12.56 (s, 1H, N2—H). Analysis calculated for C₁₇H₁₅FN₄OS₂ (374.45): C, 54.53; H, 4.04; N, 14.96. Found: C, 54.24; H, 4.09; N, 14.99. 3.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₅FN₄OS₂
M_r	374.45
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	7.9661 (6), 20.8680 (17), 10.4774 (9)
β (°)	95.257 (3)
V (Å³)	1734.4 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.33
Crystal size (mm)	0.19 × 0.15 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.663, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	18078, 3245, 2910
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.096, 1.10
No. of reflections	3245
No. of parameters	236
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23
Absolute structure	Flack (1983 )
Absolute structure parameter	0.09 (12)
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1547812

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461700671X/bt4047sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700671X/bt4047Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461700671X/bt4047Isup3.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); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

2-(5-Fluoro-1-methyl-2-oxoindolin-3-ylidene)-N-[4-(methylsulfanyl)phenyl]hydrazine-1-carbothioamide top

Crystal data top

C₁₇H₁₅FN₄OS₂	F(000) = 776
M_r = 374.45	D_x = 1.434 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 9917 reflections
a = 7.9661 (6) Å	θ = 3.2–26.4°
b = 20.8680 (17) Å	µ = 0.33 mm⁻¹
c = 10.4774 (9) Å	T = 296 K
β = 95.257 (3)°	Block, orange
V = 1734.4 (2) Å³	0.19 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2910 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θ_max = 26.4°, θ_min = 3.2°
T_min = 0.663, T_max = 0.745	h = −9→8
18078 measured reflections	k = −26→26
3245 independent reflections	l = −13→13

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0199P)² + 2.3048P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.044	(Δ/σ)_max < 0.001
wR(F²) = 0.096	Δρ_max = 0.18 e Å⁻³
S = 1.10	Δρ_min = −0.23 e Å⁻³
3245 reflections	Extinction correction: SHELXL-2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
236 parameters	Extinction coefficient: 0.016 (2)
2 restraints	Absolute structure: Flack (1983)
Hydrogen site location: mixed	Absolute structure parameter: 0.09 (12)

Special details top

Experimental. The melting point was estimated with a Buchi 540 melting-point apparatus in an open capillary and is uncorrected. Elemental analysis was performed on a Thermo Finnigan Flash EA 1112 elemental analyzer. IR spectra was recorded on a KBr disc using a Perkin– Elmer Model 1600 FT–IR spectrometer. The ¹H NMR spectra were obtained on Bruker Avance DPX 400 spectrophotometer using DMSO-d₆. All chemicals and solvents were purchased from Merck–Schuchardt and Aldrich.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

C-bound H atoms were placed in calculated positions (C—H = 0.93 Å and 0.96 Å) and N-bound H atoms were found from a difference Fourier map. All H atoms were refined using the riding-model approximation with U_iso(H) = 1.2 or 1.5 U_eq(C,N). The coordinates of the H atoms bonded to N were refined.

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

	x	y	z	U_iso*/U_eq
S1	0.7480 (2)	0.42568 (6)	0.83501 (13)	0.0655 (5)
S2	0.8897 (2)	0.76426 (7)	0.92299 (15)	0.0745 (6)
F1	0.1155 (5)	0.53841 (19)	0.0901 (3)	0.0908 (16)
O1	0.4820 (5)	0.30064 (15)	0.5192 (3)	0.0583 (13)
N1	0.3211 (5)	0.31394 (17)	0.3247 (3)	0.0492 (14)
N2	0.4943 (5)	0.44513 (16)	0.5056 (3)	0.0428 (11)
N3	0.5831 (5)	0.41981 (18)	0.6103 (3)	0.0459 (11)
N4	0.6774 (5)	0.52015 (16)	0.6595 (3)	0.0428 (10)
C1	0.2595 (6)	0.3667 (2)	0.2503 (4)	0.0452 (16)
C2	0.1575 (6)	0.3670 (3)	0.1361 (4)	0.0603 (18)
C3	0.1126 (6)	0.4254 (3)	0.0825 (4)	0.0639 (18)
C4	0.1651 (6)	0.4813 (3)	0.1437 (4)	0.0591 (19)
C5	0.2671 (6)	0.4819 (2)	0.2571 (4)	0.0503 (17)
C6	0.3147 (5)	0.4240 (2)	0.3100 (4)	0.0426 (12)
C7	0.4150 (5)	0.40606 (19)	0.4266 (4)	0.0407 (11)
C8	0.4131 (6)	0.33431 (19)	0.4325 (4)	0.0450 (14)
C9	0.2977 (8)	0.2468 (2)	0.2914 (6)	0.072 (2)
C10	0.6701 (6)	0.45967 (19)	0.6982 (4)	0.0432 (14)
C11	0.7340 (5)	0.57666 (19)	0.7249 (3)	0.0379 (11)
C12	0.8323 (6)	0.5784 (2)	0.8413 (4)	0.0467 (14)
C13	0.8783 (6)	0.6365 (2)	0.8973 (4)	0.0502 (16)
C14	0.8271 (6)	0.6943 (2)	0.8390 (4)	0.0497 (16)
C15	0.7321 (6)	0.6925 (2)	0.7212 (4)	0.0498 (14)
C16	0.6853 (6)	0.63372 (19)	0.6650 (4)	0.0448 (14)
C17	0.8004 (10)	0.8275 (3)	0.8227 (7)	0.090 (3)
H2	0.12060	0.32900	0.09680	0.0720*
H3	0.04650	0.42720	0.00470	0.0760*
H3N	0.578 (7)	0.379 (2)	0.626 (5)	0.0550*
H4N	0.621 (6)	0.529 (2)	0.583 (5)	0.0520*
H5	0.30230	0.52030	0.29620	0.0600*
H9A	0.34370	0.23840	0.21150	0.1080*
H9B	0.17950	0.23680	0.28330	0.1080*
H9C	0.35430	0.22070	0.35740	0.1080*
H12	0.86720	0.54040	0.88170	0.0560*
H13	0.94450	0.63710	0.97510	0.0600*
H15	0.69950	0.73050	0.67970	0.0600*
H16	0.62070	0.63290	0.58650	0.0540*
H17A	0.84050	0.82420	0.73930	0.1350*
H17B	0.83330	0.86820	0.86000	0.1350*
H17C	0.67980	0.82410	0.81520	0.1350*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0947 (11)	0.0465 (6)	0.0489 (6)	−0.0041 (7)	−0.0286 (6)	0.0070 (6)
S2	0.0981 (12)	0.0552 (8)	0.0695 (9)	−0.0178 (8)	0.0044 (8)	−0.0215 (7)
F1	0.086 (3)	0.104 (3)	0.078 (2)	0.023 (2)	−0.0169 (19)	0.031 (2)
O1	0.076 (3)	0.0428 (17)	0.055 (2)	−0.0027 (16)	−0.0003 (17)	0.0041 (14)
N1	0.052 (3)	0.047 (2)	0.048 (2)	−0.0094 (17)	0.0018 (18)	−0.0098 (16)
N2	0.047 (2)	0.0440 (19)	0.0349 (17)	−0.0005 (16)	−0.0093 (15)	−0.0005 (14)
N3	0.058 (2)	0.0360 (18)	0.0401 (19)	−0.0043 (16)	−0.0151 (16)	0.0027 (15)
N4	0.055 (2)	0.0383 (18)	0.0321 (16)	−0.0053 (16)	−0.0123 (15)	0.0016 (13)
C1	0.040 (3)	0.058 (3)	0.038 (2)	−0.0052 (19)	0.0055 (19)	−0.0100 (18)
C2	0.043 (3)	0.094 (4)	0.042 (2)	−0.006 (3)	−0.006 (2)	−0.021 (3)
C3	0.044 (3)	0.104 (4)	0.041 (2)	0.002 (3)	−0.011 (2)	−0.008 (3)
C4	0.046 (3)	0.083 (4)	0.047 (3)	0.012 (2)	−0.003 (2)	0.018 (2)
C5	0.047 (3)	0.054 (3)	0.048 (3)	−0.003 (2)	−0.006 (2)	0.0053 (19)
C6	0.037 (2)	0.054 (2)	0.035 (2)	−0.0059 (19)	−0.0065 (17)	−0.0047 (17)
C7	0.043 (2)	0.042 (2)	0.0356 (19)	−0.0073 (18)	−0.0044 (17)	−0.0022 (17)
C8	0.050 (3)	0.040 (2)	0.045 (2)	−0.0059 (19)	0.0037 (19)	−0.0038 (19)
C9	0.082 (4)	0.052 (3)	0.083 (4)	−0.014 (3)	0.009 (3)	−0.028 (3)
C10	0.051 (3)	0.038 (2)	0.039 (2)	−0.0008 (19)	−0.0039 (18)	−0.0011 (17)
C11	0.038 (2)	0.043 (2)	0.0323 (19)	−0.0045 (17)	0.0010 (16)	−0.0023 (16)
C12	0.051 (3)	0.043 (2)	0.044 (2)	−0.0045 (19)	−0.007 (2)	0.0008 (18)
C13	0.057 (3)	0.056 (3)	0.036 (2)	−0.010 (2)	−0.005 (2)	−0.0051 (19)
C14	0.055 (3)	0.050 (3)	0.045 (2)	−0.011 (2)	0.010 (2)	−0.0097 (19)
C15	0.059 (3)	0.041 (2)	0.049 (2)	0.0017 (19)	0.003 (2)	0.0015 (18)
C16	0.055 (3)	0.039 (2)	0.039 (2)	0.0029 (19)	−0.0030 (19)	−0.0009 (16)
C17	0.137 (7)	0.044 (3)	0.092 (4)	−0.012 (3)	0.022 (4)	−0.013 (3)

Geometric parameters (Å, º) top

S1—C10	1.667 (4)	C6—C7	1.446 (6)
S2—C14	1.753 (4)	C7—C8	1.499 (6)
S2—C17	1.793 (7)	C11—C16	1.385 (6)
F1—C4	1.361 (7)	C11—C12	1.388 (5)
O1—C8	1.236 (5)	C12—C13	1.382 (6)
N1—C1	1.411 (5)	C13—C14	1.396 (6)
N1—C8	1.357 (5)	C14—C15	1.388 (6)
N1—C9	1.452 (6)	C15—C16	1.397 (6)
N2—N3	1.357 (5)	C2—H2	0.9300
N2—C7	1.286 (5)	C3—H3	0.9300
N3—C10	1.380 (6)	C5—H5	0.9300
N4—C10	1.329 (5)	C9—H9A	0.9600
N4—C11	1.417 (5)	C9—H9B	0.9600
C1—C2	1.383 (6)	C9—H9C	0.9600
C1—C6	1.401 (6)	C12—H12	0.9300
C2—C3	1.375 (8)	C13—H13	0.9300
C3—C4	1.378 (8)	C15—H15	0.9300
N3—H3N	0.87 (4)	C16—H16	0.9300
N4—H4N	0.90 (5)	C17—H17A	0.9600
C4—C5	1.377 (6)	C17—H17B	0.9600
C5—C6	1.368 (6)	C17—H17C	0.9600

C14—S2—C17	103.9 (3)	N4—C11—C12	125.2 (4)
C1—N1—C8	110.5 (3)	C11—C12—C13	120.2 (4)
C1—N1—C9	126.2 (4)	C12—C13—C14	121.1 (4)
C8—N1—C9	123.4 (4)	S2—C14—C13	116.2 (3)
N3—N2—C7	117.6 (3)	C13—C14—C15	118.7 (4)
N2—N3—C10	119.9 (4)	S2—C14—C15	125.2 (3)
C10—N4—C11	131.6 (3)	C14—C15—C16	120.1 (4)
N1—C1—C2	128.9 (4)	C11—C16—C15	120.8 (4)
N1—C1—C6	109.9 (4)	C1—C2—H2	121.00
C2—C1—C6	121.2 (4)	C3—C2—H2	121.00
C1—C2—C3	117.9 (5)	C2—C3—H3	120.00
C2—C3—C4	120.3 (4)	C4—C3—H3	120.00
N2—N3—H3N	120 (3)	C4—C5—H5	121.00
C10—N3—H3N	120 (4)	C6—C5—H5	121.00
F1—C4—C3	119.0 (4)	N1—C9—H9A	110.00
C10—N4—H4N	116 (3)	N1—C9—H9B	110.00
F1—C4—C5	118.3 (5)	N1—C9—H9C	109.00
C3—C4—C5	122.7 (5)	H9A—C9—H9B	109.00
C11—N4—H4N	112 (3)	H9A—C9—H9C	109.00
C4—C5—C6	117.5 (4)	H9B—C9—H9C	109.00
C1—C6—C5	120.6 (4)	C11—C12—H12	120.00
C1—C6—C7	106.4 (4)	C13—C12—H12	120.00
C5—C6—C7	133.0 (4)	C12—C13—H13	119.00
N2—C7—C8	127.8 (4)	C14—C13—H13	119.00
C6—C7—C8	106.7 (3)	C14—C15—H15	120.00
N2—C7—C6	125.5 (4)	C16—C15—H15	120.00
O1—C8—N1	127.1 (4)	C11—C16—H16	120.00
O1—C8—C7	126.3 (4)	C15—C16—H16	120.00
N1—C8—C7	106.6 (3)	S2—C17—H17A	109.00
N3—C10—N4	113.7 (4)	S2—C17—H17B	109.00
S1—C10—N3	116.2 (3)	S2—C17—H17C	110.00
S1—C10—N4	130.0 (3)	H17A—C17—H17B	109.00
N4—C11—C16	115.7 (3)	H17A—C17—H17C	110.00
C12—C11—C16	119.2 (4)	H17B—C17—H17C	109.00

C17—S2—C14—C15	0.8 (5)	C1—C2—C3—C4	−1.7 (7)
C17—S2—C14—C13	−179.1 (4)	C2—C3—C4—F1	−178.4 (4)
C9—N1—C1—C2	4.2 (8)	C2—C3—C4—C5	2.0 (7)
C8—N1—C1—C6	0.9 (5)	C3—C4—C5—C6	−0.9 (7)
C8—N1—C1—C2	−178.1 (5)	F1—C4—C5—C6	179.6 (4)
C9—N1—C8—C7	176.4 (4)	C4—C5—C6—C1	−0.5 (7)
C1—N1—C8—O1	178.5 (5)	C4—C5—C6—C7	−178.3 (4)
C9—N1—C1—C6	−176.8 (5)	C1—C6—C7—C8	−0.8 (5)
C1—N1—C8—C7	−1.4 (5)	C1—C6—C7—N2	176.8 (4)
C9—N1—C8—O1	−3.7 (8)	C5—C6—C7—C8	177.2 (5)
N3—N2—C7—C6	−179.8 (4)	C5—C6—C7—N2	−5.1 (8)
C7—N2—N3—C10	−179.8 (4)	C6—C7—C8—O1	−178.5 (5)
N3—N2—C7—C8	−2.6 (7)	C6—C7—C8—N1	1.3 (5)
N2—N3—C10—N4	−9.6 (6)	N2—C7—C8—O1	3.9 (8)
N2—N3—C10—S1	170.0 (3)	N2—C7—C8—N1	−176.2 (4)
C10—N4—C11—C12	15.7 (7)	N4—C11—C16—C15	179.3 (4)
C11—N4—C10—S1	−8.7 (8)	C12—C11—C16—C15	−0.9 (7)
C11—N4—C10—N3	170.8 (4)	N4—C11—C12—C13	−179.1 (4)
C10—N4—C11—C16	−164.5 (5)	C16—C11—C12—C13	1.1 (7)
N1—C1—C2—C3	179.2 (4)	C11—C12—C13—C14	0.2 (7)
C2—C1—C6—C7	179.1 (4)	C12—C13—C14—C15	−1.7 (7)
N1—C1—C6—C7	0.0 (5)	C12—C13—C14—S2	178.3 (4)
C6—C1—C2—C3	0.4 (7)	S2—C14—C15—C16	−178.1 (4)
C2—C1—C6—C5	0.8 (7)	C13—C14—C15—C16	1.9 (7)
N1—C1—C6—C5	−178.3 (4)	C14—C15—C16—C11	−0.6 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1	0.87 (4)	2.09 (5)	2.757 (5)	133 (5)
N4—H4N···N2	0.90 (5)	2.14 (5)	2.598 (5)	110 (3)
C3—H3···S1ⁱ	0.93	2.84	3.712 (5)	158
C9—H9B···S2ⁱⁱ	0.96	2.84	3.652 (7)	142
C9—H9C···O1	0.96	2.52	2.911 (7)	104
C12—H12···S1	0.93	2.61	3.256 (4)	128

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

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.

Funding information

Funding for this research was provided by: TÜBİTAK (award No. 1003–215S011).

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