Synthesis and crystal structure analysis of 1-ethyl-1,3-di­hydro-2H-benzo[d]imidazole-2-thione

Gurbanov, A.V.; Guseinov, F.I.; Samigullina, A.I.; Hökelek, T.; Hasanov, K.I.; Javadzade, T.A.; Belay, A.N.

doi:10.1107/S2056989025000519

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ISSN: 2056-9890

Volume 81| Part 2| February 2025| Pages 169-171

https://doi.org/10.1107/S2056989025000519

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Synthesis and crystal structure analysis of 1-ethyl-1,3-dihydro-2H-benzo[d]imidazole-2-thione

Atash V. Gurbanov,^a,^b Firudin I. Guseinov,^b,^c Aida I. Samigullina,^c Tuncer Hökelek,^d Khudayar I. Hasanov,^e,^f Tahir A. Javadzade ^g and Alebel N. Belay ^h ^*

^aExcellence Center, Baku State University, Z. Xalilov Str. 23, AZ 1148 Baku, Azerbaijan, ^bKosygin State University of Russia, 117997 Moscow, Russian Federation, ^cN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation, ^dHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, ^eWestern Caspian University, Istiglaliyyat Str. 31, AZ 1001 Baku, Azerbaijan, ^fAzerbaijan Medical University, Scientific Research Centre (SRC), A. Kasumzade Str. 14, AZ 1022 Baku, Azerbaijan, ^gDepartment of Chemistry and Chemical Engineering, Khazar University, Mahzati Str. 41, AZ 1096 Baku, Azerbaijan, and ^hDepartment of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia
^*Correspondence e-mail: alebel.nibret@bdu.edu.et

Edited by S. Parkin, University of Kentucky, USA (Received 9 December 2024; accepted 20 January 2025; online 28 January 2025)

The asymmetric unit of the title compound, C₉H₁₀N₂S, contains two crystallographically independent, almost planar, molecules. In the crystal, intermolecular N—H⋯S hydrogen bonds link the molecules into pseudocentrosymmetric dimers, enclosing R₂²(8) ring motifs. There are mutual π–π interactions between the five- and six-membered rings of each independent molecule in the chosen asymmetric unit, with ring centroid-to-centroid distances of 3.6685 (12) and 3.7062 (12) Å. A weak C—H⋯π(ring) interaction is also observed. The N—H⋯S hydrogen bonds, the π–π interactions and the weak C—H⋯π(ring) interaction are effective in the stabilization of the crystal structure. The structure was refined as an inversion twin with a component occupancy ratio of 0.546 (15):0.454 (16).

Keywords: noncovalent interactions; hydrogen bonding; crystal structure.

CCDC reference: 2418168

1. Chemical context

Benzimidazoles are defined as a class of heterocyclic aromatic organic compounds characterized by a benzene ring fused to an imidazole ring at specific positions, exhibiting both acidic and weakly basic properties (Gaba et al., 2014 ). Benzimidazole and its derivatives have attracted considerable interest in recent years for their versatile properties in chemistry and pharmacology (Akhtar et al., 2017 ; Khalilov et al., 2024 ). They are used as auxilliary ligands in the synthesis of coordination compounds (Jlassi et al., 2014 ; Mizar et al., 2012 ). Thus, benzimidazole compounds have been an interesting resource for researchers for more than a century (Guseinov et al., 2006 , 2017 , 2020 ; Rzayev & Khalilov, 2024 ). For instance, 2-mercaptobenzimidazole was successfully built into zeolitic imidazolate framework-8 on graphene oxide nanosheets and then embedded into an epoxy coating to prepare a composite coating with pH-responsive and self-healing performance (Li et al., 2021 ). The attachment of noncovalent halogen-bond donor or acceptor site(s) to benzimidazole can be used as a synthetic strategy in the design of catalysts, materials and drugs (Ma et al., 2021 ; Mahmoudi et al., 2017a ,b ; Shixaliyev et al., 2014 ). Herein, we have synthesized 1-ethyl-1,3-dihydro-2H-benzo[d]imidazole-2-thione by the reaction of N¹-ethylbenzene-1,2-diamine with carbon disulfide in the presence of pyridine (see Scheme) and studied its molecular and crystal structures.

2. Structural commentary

The asymmetric unit of the title structure contains two crystallographically independent molecules (Fig. 1). The planar A (atoms C4a–C9a), B (N1a/N3a/C2a/C4a/C9a), C (C4b–C9b) and D (N1b/N3b/C2b/C4b/C9b) rings are oriented at dihedral angles of A/B = 0.75 (9)° and C/D = 1.64 (12)°. Thus, they are almost coplanar. On the other hand, atoms S2a/C10a and S2b/C10b are 0.0061 (3)/−0.1824 (15) and 0.0864 (4)/−0.0278 (15) Å away from the best least-squares planes of the B and D rings, respectively. Thus, they are almost coplanar with the corresponding ring planes. The orientations of the ethyl groups relative to the benzimidazole fused rings may be described by the torsion angles C2a—N3a—C10a—C11a = 91.4 (2)°, C4a—N3a—C10a—C11a = −98.0 (2)°, C2b—N3b—C10b—C11b = 94.4 (2)° and C4b–N3b—C10b—C11b = −84.5 (2)°. There no unusual bond distances or interbond angles in the molecules. The structure was refined as an inversion twin with a component occupancy ratio of 0.546 (15):0.454 (16).

Figure 1
The title molecules with the atom-numbering scheme and 50% probability ellipsoids.

3. Supramolecular features

In the crystal, intermolecular N—H⋯S hydrogen bonds (Table 1) link the molecules into pseudocentrosymmetric dimers, enclosing R₂²(8) ring motifs, where the molecules are stacked along the a-axis direction (Fig. 2). There are π–π interactions between the B and C rings, and between the A and D rings, with centroid-to-centroid distances of 3.6685 (12) [dihedral = 11.02 (10)° and slippage = 0.413 Å] and 3.7062 (12) Å [dihedral = 11.26 (11)° and slippage = 0.405 Å], respectively. A weak C—H⋯π(ring) interaction is also observed (Table 1). The N—H⋯S hydrogen bonds, the π–π interactions and the weak C—H⋯π(ring) interaction are effective in the stabilization of the crystal structure.

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C4A⋯C9A ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1B—H1B⋯S2Aⁱ	0.84 (3)	2.49 (3)	3.3258 (18)	171 (3)
N1A—H1A⋯S2Bⁱⁱ	0.88 (3)	2.41 (3)	3.2654 (18)	165 (3)
C6B—H6B⋯Cg3ⁱⁱⁱ	0.95	2.85	3.6470 (17)	143
Symmetry codes: (i) ; (ii) ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A partial packing diagram. Intermolecular N—H⋯S hydrogen bonds are shown as dashed lines.

4. Synthesis and crystallization

CS₂ (228 mg, 3.00 mmol) was added to a solution of N¹-ethylbenzene-1,2-diamine (136 mg, 1.00 mmol) in pyridine (10 ml) and the resulting solution refluxed for 8 h. The reaction mixture was then evaporated in a vacuum and the residue crystallized from ethanol. The title compound was obtained in the form of orange crystals (yield: 146 mg, 82%; m.p. 120–122 °C) which were soluble in methanol, ethanol and dimethyl sulfoxide (DMSO). Analysis calculated (%) for C₉H₁₀N₂S: C 60.64, H 5.65, N 15.72; found: C 60.61, H 5.65, N 15.69. ¹H NMR (300 MHz, DMSO-d₆): δ 1.19 (3H, CH₃), 3.82 (2H, CH₂), 6.83–7.08 (4H, Ar-H), 10.87 (1H, NH). ¹³C NMR (75 MHz, DMSO-d₆): δ 13.8, 34.8, 107.9, 108.8, 120.4, 120.6, 128.3, 129.8, 153.9.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH hydrogens were located in a difference Fourier map and refined freely. The C-bound H-atom positions were calculated geometrically at distances of 0.95 (for aromatic CH), 0.99 (for CH₂) and 0.98 Å (for CH₃), and refined using a riding model by applying the constraint U_iso(H) = kU_eq(C), where k = 1.5 for methyl H atoms and 1.2 for the other H atoms. The title compound was refined as an inversion twin with component ratio occupancies of 0.546 (15):0.454 (16).

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂S
M_r	178.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.4512 (5), 14.77990 (12), 15.89120 (11)
V (Å³)	1750.06 (12)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	2.80
Crystal size (mm)	0.41 × 0.24 × 0.17

Data collection
Diffractometer	Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.405, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23801, 3799, 3779
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.069, 1.06
No. of reflections	3799
No. of parameters	229
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.454 (16)
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2418168

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989025000519/pk2714sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025000519/pk2714Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025000519/pk2714Isup3.cml

checkCIF report

Computing details top

1-Ethyl-1,3-dihydro-2H-benzo[d]imidazole-2-thione top

Crystal data top

C₉H₁₀N₂S	D_x = 1.353 Mg m⁻³
M_r = 178.25	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 18990 reflections
a = 7.4512 (5) Å	θ = 4.1–79.0°
b = 14.77990 (12) Å	µ = 2.80 mm⁻¹
c = 15.89120 (11) Å	T = 100 K
V = 1750.06 (12) Å³	Block, colorless
Z = 8	0.41 × 0.24 × 0.17 mm
F(000) = 752

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	3799 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3779 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.035
Detector resolution: 10.0000 pixels mm^-1	θ_max = 79.5°, θ_min = 4.1°
ω scans	h = −9→9
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2023)	k = −18→18
T_min = 0.405, T_max = 1.000	l = −15→20
23801 measured reflections

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)] = 0.026	w = 1/[σ²(F_o²) + (0.0359P)² + 0.5853P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.069	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.25 e Å⁻³
3799 reflections	Δρ_min = −0.21 e Å⁻³
229 parameters	Extinction correction: SHELXL2018 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0010 (2)
Primary atom site location: dual	Absolute structure: Refined as an inversion twin.
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.454 (16)

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. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
S2A	−0.22204 (7)	0.21363 (3)	0.89250 (3)	0.02146 (13)
N1A	−0.0479 (2)	0.19722 (11)	0.74247 (10)	0.0187 (3)
N3A	0.1123 (2)	0.15428 (11)	0.85066 (10)	0.0173 (3)
C2A	−0.0506 (3)	0.18841 (13)	0.82739 (12)	0.0182 (4)
C4A	0.2181 (3)	0.14132 (12)	0.77941 (12)	0.0177 (4)
C5A	0.3909 (3)	0.10730 (14)	0.76978 (14)	0.0218 (4)
H5A	0.459639	0.087262	0.816552	0.026*
C6A	0.4579 (3)	0.10412 (14)	0.68818 (15)	0.0250 (4)
H6A	0.575684	0.081670	0.678910	0.030*
C7A	0.3556 (3)	0.13326 (14)	0.61921 (14)	0.0234 (4)
H7A	0.405983	0.130237	0.564370	0.028*
C8A	0.1826 (3)	0.16641 (14)	0.62913 (13)	0.0218 (4)
H8A	0.112969	0.185807	0.582421	0.026*
C9A	0.1164 (3)	0.16980 (13)	0.71074 (13)	0.0180 (4)
C10A	0.1735 (3)	0.14556 (14)	0.93791 (13)	0.0212 (4)
H10A	0.117518	0.193980	0.972037	0.025*
H10B	0.305098	0.154553	0.939713	0.025*
C11A	0.1290 (3)	0.05472 (14)	0.97697 (14)	0.0247 (4)
H11A	0.182860	0.006293	0.943261	0.037*
H11B	−0.001560	0.046798	0.978545	0.037*
H11C	0.176860	0.052327	1.034369	0.037*
S2B	0.71248 (7)	0.32708 (3)	0.61994 (3)	0.02249 (13)
N1B	0.5206 (2)	0.33699 (12)	0.76571 (11)	0.0201 (3)
N3B	0.3941 (2)	0.40686 (11)	0.65996 (11)	0.0188 (3)
C2B	0.5411 (3)	0.35762 (13)	0.68320 (13)	0.0189 (4)
C4B	0.2768 (3)	0.41420 (13)	0.72778 (12)	0.0189 (4)
C5B	0.1079 (3)	0.45342 (14)	0.73544 (14)	0.0229 (4)
H5B	0.051416	0.482733	0.689295	0.028*
C6B	0.0258 (3)	0.44772 (14)	0.81367 (15)	0.0259 (4)
H6B	−0.089939	0.473475	0.821187	0.031*
C7B	0.1094 (3)	0.40496 (14)	0.88166 (14)	0.0247 (4)
H7B	0.049496	0.402837	0.934396	0.030*
C8B	0.2777 (3)	0.36553 (13)	0.87409 (13)	0.0218 (4)
H8B	0.334784	0.336867	0.920438	0.026*
C9B	0.3587 (3)	0.37001 (13)	0.79548 (13)	0.0191 (4)
C10B	0.3654 (3)	0.44431 (14)	0.57602 (13)	0.0205 (4)
H10C	0.483111	0.454711	0.548751	0.025*
H10D	0.304031	0.503466	0.581024	0.025*
C11B	0.2538 (3)	0.38201 (15)	0.52124 (13)	0.0262 (5)
H11D	0.238632	0.409231	0.465462	0.039*
H11E	0.135862	0.372960	0.547203	0.039*
H11F	0.314744	0.323560	0.515652	0.039*
H1B	0.596 (4)	0.308 (2)	0.7946 (19)	0.034 (8)*
H1A	−0.130 (4)	0.225 (2)	0.7125 (19)	0.032 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2A	0.0218 (2)	0.0243 (2)	0.0183 (2)	0.00626 (19)	0.00212 (18)	0.00069 (17)
N1A	0.0183 (8)	0.0205 (8)	0.0173 (8)	0.0042 (7)	−0.0001 (6)	0.0007 (6)
N3A	0.0185 (8)	0.0153 (7)	0.0181 (8)	0.0005 (6)	−0.0010 (6)	−0.0004 (6)
C2A	0.0201 (9)	0.0145 (8)	0.0198 (9)	0.0009 (7)	−0.0014 (8)	−0.0011 (7)
C4A	0.0185 (9)	0.0128 (8)	0.0217 (9)	−0.0010 (7)	−0.0005 (8)	−0.0008 (7)
C5A	0.0184 (9)	0.0187 (9)	0.0282 (10)	0.0007 (8)	−0.0021 (8)	0.0015 (8)
C6A	0.0193 (9)	0.0202 (10)	0.0354 (12)	0.0022 (8)	0.0051 (9)	−0.0005 (8)
C7A	0.0254 (10)	0.0195 (9)	0.0253 (10)	−0.0012 (8)	0.0066 (9)	−0.0002 (8)
C8A	0.0239 (10)	0.0193 (9)	0.0222 (9)	0.0004 (8)	0.0014 (8)	0.0012 (7)
C9A	0.0179 (9)	0.0143 (8)	0.0219 (9)	0.0005 (7)	0.0003 (7)	−0.0012 (7)
C10A	0.0232 (10)	0.0211 (9)	0.0193 (9)	−0.0003 (8)	−0.0058 (8)	−0.0004 (7)
C11A	0.0275 (11)	0.0226 (10)	0.0241 (10)	0.0020 (9)	−0.0021 (9)	0.0022 (8)
S2B	0.0200 (2)	0.0253 (2)	0.0222 (2)	0.00355 (19)	0.00136 (18)	0.00493 (18)
N1B	0.0196 (8)	0.0205 (8)	0.0203 (8)	0.0035 (7)	−0.0015 (7)	0.0033 (6)
N3B	0.0190 (7)	0.0164 (7)	0.0210 (8)	0.0012 (6)	−0.0031 (7)	0.0015 (6)
C2B	0.0185 (9)	0.0152 (8)	0.0229 (9)	0.0000 (7)	−0.0046 (8)	0.0017 (7)
C4B	0.0202 (9)	0.0144 (8)	0.0221 (9)	−0.0014 (8)	−0.0016 (8)	0.0007 (7)
C5B	0.0220 (10)	0.0174 (9)	0.0294 (11)	0.0027 (8)	−0.0034 (9)	0.0010 (8)
C6B	0.0235 (10)	0.0192 (9)	0.0351 (12)	0.0030 (8)	0.0034 (9)	−0.0019 (8)
C7B	0.0288 (10)	0.0191 (9)	0.0263 (10)	−0.0014 (8)	0.0046 (9)	−0.0025 (8)
C8B	0.0261 (10)	0.0174 (9)	0.0219 (9)	−0.0017 (8)	−0.0006 (8)	0.0009 (7)
C9B	0.0197 (9)	0.0144 (8)	0.0231 (9)	−0.0008 (7)	−0.0017 (8)	−0.0003 (7)
C10B	0.0220 (9)	0.0188 (9)	0.0206 (9)	−0.0005 (8)	−0.0037 (8)	0.0044 (7)
C11B	0.0286 (11)	0.0259 (10)	0.0241 (10)	−0.0033 (9)	−0.0066 (9)	0.0001 (8)

Geometric parameters (Å, º) top

S2A—C2A	1.686 (2)	S2B—C2B	1.687 (2)
N1A—C2A	1.356 (3)	N1B—C2B	1.355 (3)
N1A—C9A	1.385 (3)	N1B—C9B	1.385 (3)
N1A—H1A	0.88 (3)	N1B—H1B	0.84 (3)
N3A—C2A	1.365 (3)	N3B—C2B	1.366 (3)
N3A—C4A	1.393 (3)	N3B—C4B	1.392 (3)
N3A—C10A	1.465 (2)	N3B—C10B	1.460 (2)
C4A—C5A	1.391 (3)	C4B—C5B	1.391 (3)
C4A—C9A	1.394 (3)	C4B—C9B	1.399 (3)
C5A—H5A	0.9500	C5B—H5B	0.9500
C5A—C6A	1.390 (3)	C5B—C6B	1.388 (3)
C6A—H6A	0.9500	C6B—H6B	0.9500
C6A—C7A	1.403 (3)	C6B—C7B	1.398 (3)
C7A—H7A	0.9500	C7B—H7B	0.9500
C7A—C8A	1.388 (3)	C7B—C8B	1.388 (3)
C8A—H8A	0.9500	C8B—H8B	0.9500
C8A—C9A	1.388 (3)	C8B—C9B	1.389 (3)
C10A—H10A	0.9900	C10B—H10C	0.9900
C10A—H10B	0.9900	C10B—H10D	0.9900
C10A—C11A	1.516 (3)	C10B—C11B	1.516 (3)
C11A—H11A	0.9800	C11B—H11D	0.9800
C11A—H11B	0.9800	C11B—H11E	0.9800
C11A—H11C	0.9800	C11B—H11F	0.9800

C2A—N1A—C9A	110.32 (17)	C2B—N1B—C9B	110.45 (17)
C2A—N1A—H1A	125.1 (19)	C2B—N1B—H1B	125 (2)
C9A—N1A—H1A	123.7 (19)	C9B—N1B—H1B	125 (2)
C2A—N3A—C4A	109.50 (16)	C2B—N3B—C4B	109.61 (16)
C2A—N3A—C10A	124.42 (16)	C2B—N3B—C10B	124.51 (18)
C4A—N3A—C10A	125.52 (17)	C4B—N3B—C10B	125.87 (17)
N1A—C2A—S2A	126.93 (16)	N1B—C2B—S2B	127.00 (15)
N1A—C2A—N3A	106.97 (17)	N1B—C2B—N3B	106.95 (18)
N3A—C2A—S2A	126.10 (15)	N3B—C2B—S2B	126.05 (16)
N3A—C4A—C9A	106.69 (17)	N3B—C4B—C9B	106.57 (17)
C5A—C4A—N3A	131.55 (19)	C5B—C4B—N3B	131.94 (19)
C5A—C4A—C9A	121.76 (19)	C5B—C4B—C9B	121.5 (2)
C4A—C5A—H5A	121.7	C4B—C5B—H5B	121.6
C6A—C5A—C4A	116.6 (2)	C6B—C5B—C4B	116.9 (2)
C6A—C5A—H5A	121.7	C6B—C5B—H5B	121.6
C5A—C6A—H6A	119.2	C5B—C6B—H6B	119.2
C5A—C6A—C7A	121.6 (2)	C5B—C6B—C7B	121.5 (2)
C7A—C6A—H6A	119.2	C7B—C6B—H6B	119.2
C6A—C7A—H7A	119.2	C6B—C7B—H7B	119.2
C8A—C7A—C6A	121.6 (2)	C8B—C7B—C6B	121.7 (2)
C8A—C7A—H7A	119.2	C8B—C7B—H7B	119.2
C7A—C8A—H8A	121.7	C7B—C8B—H8B	121.6
C7A—C8A—C9A	116.66 (19)	C7B—C8B—C9B	116.77 (19)
C9A—C8A—H8A	121.7	C9B—C8B—H8B	121.6
N1A—C9A—C4A	106.50 (17)	N1B—C9B—C4B	106.37 (18)
N1A—C9A—C8A	131.66 (19)	N1B—C9B—C8B	131.99 (19)
C8A—C9A—C4A	121.84 (18)	C8B—C9B—C4B	121.64 (19)
N3A—C10A—H10A	108.9	N3B—C10B—H10C	109.2
N3A—C10A—H10B	108.9	N3B—C10B—H10D	109.2
N3A—C10A—C11A	113.41 (17)	N3B—C10B—C11B	112.01 (17)
H10A—C10A—H10B	107.7	H10C—C10B—H10D	107.9
C11A—C10A—H10A	108.9	C11B—C10B—H10C	109.2
C11A—C10A—H10B	108.9	C11B—C10B—H10D	109.2
C10A—C11A—H11A	109.5	C10B—C11B—H11D	109.5
C10A—C11A—H11B	109.5	C10B—C11B—H11E	109.5
C10A—C11A—H11C	109.5	C10B—C11B—H11F	109.5
H11A—C11A—H11B	109.5	H11D—C11B—H11E	109.5
H11A—C11A—H11C	109.5	H11D—C11B—H11F	109.5
H11B—C11A—H11C	109.5	H11E—C11B—H11F	109.5

N3A—C4A—C5A—C6A	−179.6 (2)	N3B—C4B—C5B—C6B	179.4 (2)
N3A—C4A—C9A—N1A	−1.1 (2)	N3B—C4B—C9B—N1B	−0.7 (2)
N3A—C4A—C9A—C8A	179.75 (18)	N3B—C4B—C9B—C8B	179.23 (18)
C2A—N1A—C9A—C4A	1.1 (2)	C2B—N1B—C9B—C4B	−0.8 (2)
C2A—N1A—C9A—C8A	−179.9 (2)	C2B—N1B—C9B—C8B	179.3 (2)
C2A—N3A—C4A—C5A	−178.9 (2)	C2B—N3B—C4B—C5B	−176.8 (2)
C2A—N3A—C4A—C9A	0.8 (2)	C2B—N3B—C4B—C9B	1.9 (2)
C2A—N3A—C10A—C11A	91.4 (2)	C2B—N3B—C10B—C11B	94.4 (2)
C4A—N3A—C2A—S2A	179.34 (14)	C4B—N3B—C2B—S2B	176.59 (15)
C4A—N3A—C2A—N1A	−0.2 (2)	C4B—N3B—C2B—N1B	−2.3 (2)
C4A—N3A—C10A—C11A	−98.0 (2)	C4B—N3B—C10B—C11B	−84.5 (2)
C4A—C5A—C6A—C7A	−0.4 (3)	C4B—C5B—C6B—C7B	0.3 (3)
C5A—C4A—C9A—N1A	178.60 (17)	C5B—C4B—C9B—N1B	178.17 (18)
C5A—C4A—C9A—C8A	−0.5 (3)	C5B—C4B—C9B—C8B	−1.9 (3)
C5A—C6A—C7A—C8A	−0.2 (3)	C5B—C6B—C7B—C8B	−0.5 (3)
C6A—C7A—C8A—C9A	0.4 (3)	C6B—C7B—C8B—C9B	−0.5 (3)
C7A—C8A—C9A—N1A	−178.9 (2)	C7B—C8B—C9B—N1B	−178.5 (2)
C7A—C8A—C9A—C4A	−0.1 (3)	C7B—C8B—C9B—C4B	1.7 (3)
C9A—N1A—C2A—S2A	179.93 (14)	C9B—N1B—C2B—S2B	−176.99 (15)
C9A—N1A—C2A—N3A	−0.6 (2)	C9B—N1B—C2B—N3B	1.9 (2)
C9A—C4A—C5A—C6A	0.7 (3)	C9B—C4B—C5B—C6B	0.9 (3)
C10A—N3A—C2A—S2A	−8.8 (3)	C10B—N3B—C2B—S2B	−2.5 (3)
C10A—N3A—C2A—N1A	171.69 (17)	C10B—N3B—C2B—N1B	178.59 (18)
C10A—N3A—C4A—C5A	9.4 (3)	C10B—N3B—C4B—C5B	2.3 (3)
C10A—N3A—C4A—C9A	−170.92 (17)	C10B—N3B—C4B—C9B	−179.08 (18)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C4A···C9A ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H1B···S2Aⁱ	0.84 (3)	2.49 (3)	3.3258 (18)	171 (3)
N1A—H1A···S2Bⁱⁱ	0.88 (3)	2.41 (3)	3.2654 (18)	165 (3)
C6B—H6B···Cg3ⁱⁱⁱ	0.95	2.85	3.6470 (17)	143

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

Acknowledgements

Crystal structure determination was performed in the Department of Structural Studies of the Zelinsky Institute of Organic Chemistry, Moscow. This work was supported by Baku State University, Western Caspian University, Azerbaijan Medical University and Khazar University in Azerbaijan. TH is also grateful to Hacettepe University Scientific Research Project Unit. The contributions of the author are as follows: conceptualization AVG, TH and ANB; synthesis AVG and FIG; X-ray analysis AIS; writing (review and editing of the manuscript) AVG and TH; funding acquisition AVG, KIH and TAJ; supervision AVG, TH and ANB.

Funding information

Funding for this research was provided by: Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004 to T. Hökelek).

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