Crystal structure and Hirshfeld surface analysis of 5-(5-phenyl-1,2-oxazol-3-yl)-1,3,4-thia­diazol-2-amine

Nikitina, E.V.; Çelikesir, S.T.; Akkurt, M.; Petkevich, S.K.; Akishina, E.A.; Khrustalev, V.N.; Mlowe, S.

doi:10.1107/S2056989022003450

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ISSN: 2056-9890

Volume 78| Part 4| April 2022| Pages 453-457

https://doi.org/10.1107/S2056989022003450

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Crystal structure and Hirshfeld surface analysis of 5-(5-phenyl-1,2-oxazol-3-yl)-1,3,4-thiadiazol-2-amine

Evgeniya V. Nikitina,^a Sevim Türktekin Çelikesir,^b Mehmet Akkurt,^b Sergey K. Petkevich,^c Ekaterina A. Akishina,^c Victor N. Khrustalev ^a,^d and Sixberth Mlowe ^e ^*

^aDepartment of Organic Chemistry, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., 117198, Moscow, Russian Federation, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cLaboratory of the Chemistry of Heterocyclic Compounds, Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 13, Surganova Str., 220072, Minsk, Belarus, ^dN.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Av., Moscow, Russian Federation, and ^eUniversity of Dar es Salaam, Dar es Salaam University College of Education, Department of Chemistry, PO Box 2329, Dar es Salaam, Tanzania
^*Correspondence e-mail: sixberth.mlowe@duce.ac.tz

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 22 March 2022; accepted 27 March 2022; online 31 March 2022)

The title compound, C₁₁H₈N₄OS, crystallizes with two independent molecules in the asymmetric unit. In the crystal, the N—H⋯N and C—H⋯N hydrogen bonds connect the molecules, generating double layers parallel to the (001) plane. The layers are joined by C—H⋯π interactions to form a three-dimensional supramolecular structure.

Keywords: crystal structure; hydrogen bonds; C—H⋯π interactions; π–π stacking interactions; Hirshfeld surface analysis.

CCDC reference: 2162503

1. Chemical context

Compounds with the five-membered isoxazole, isothiazole and 1,3,4-thiadiazole heterocycles possess high potential for biological activity and are privileged scaffolds for the development of pharmaceutical agents (Das & Chanda, 2021 ; Kletskov et al., 2020 ; Khalilullah et al., 2014 ; Yadigarov et al., 2009 ; Safavora et al., 2019 ; Zubkov et al., 2014 ). In particular, isoxazoles are able to enhance the action of `first-line' antitumor substances, which makes it possible to reduce their therapeutic doses and thus reduce toxic side effects (Khalilov et al., 2021 ; Kulchitsky et al., 2012 ; Naghiyev et al., 2020 ). The combination of the pharmacophore fragments of isoxazole and thiadiazole in one molecule increases the variability of its binding to the key sites of enzymes regulating the biological action. The presence of an amino group additionally increases the biopotential of the molecule, and the introduction of an aromatic fragment makes it possible to implement binding with a biotarget by π-stacking (Shixaliyev et al., 2014 , 2018 ; Mahmudov et al., 2011 , 2013 ; Gurbanov et al., 2017 , 2018a ,b ). To assess the biological potential of a molecule in silico and the molecular docking procedure, which is widely used for the development of new pharmaceuticals, information about the structures of promising molecules is needed. All this initiated our research on the synthesis of 5-(5-phenylisoxazol-3-yl)-1,3,4-thiadiazol-2-amine (1) and the further determination of the accurate structure of its molecule. The synthesis and structure of the compound has not published before. There are many approaches for building a thiadiazole heterocycle based on the use of carboxylic acids (Bhinge et al., 2015 ; Nayak et al., 2014 ), carbonyl chlorides (Sun et al., 2001 ; Kudelko et al., 2020 ), aldehydes (Shivakumara et al., 2019 ; Wang et al., 2019 ), etc. We chose here a method based on the transformation of carbonitriles (as shown in the scheme) as the shortest and most convenient way to achieve this purpose (Sakthivel et al., 2016 ; et al.; Abdelhamid et al., 2011 ). Its efficacy has recently been demonstrated by one of us (Petkevich et al., 2021 ). The synthetic procedure involves the interaction of 5-phenylisoxazole-3-carbonitrile with thiosemicarbazide. The starting 5-phenylisoxazole-3-carbonitrile was obtained according to the previously described method (Kulchitsky et al., 2012; Bumagin et al., 2018 ).

2. Structural commentary

The title compound 1 crystallizes in the orthorhombic space group Pca2₁, with two independent molecules (I with S1 and II with S2) in the asymmetric unit (Fig. 1). The oxazole (O1/N2/C3/C4/C5 and O12/N13/C14/C15/C16) and thiadiazole (S1/N3/N4/C1/C2 and S2/N14/N15/C12/C13) rings are essentially planar and inclined to one another by 18.8 (3) and 14.6 (3)° in molecules I and II, respectively. The phenyl rings (C6–C11 and C17–C22) make dihedral angles of 24.6 (3) and 26.8 (3)° with the oxazole rings in molecules I and II, respectively. Fig. 2 shows the overlay of molecules I and II in the asymmetric unit, with an r.m.s. deviation of 0.087 Å. The C—N bond distances to the amino N atom of 1.330 (6) and 1.328 (6) Å, respectively, in molecules I and II indicate strong conjugation of the amino groups with the thiadiazole π-systems.

Figure 1
View of the two independent molecules, I and II, in the asymmetric unit of the title compound, with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level.

Figure 2
Overlay image of two independent molecules in the asymmetric unit of the title compound.

3. Supramolecular features

In the crystal, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds (Table 1, Figs. 3 and 4), forming double layers of cross-linked molecules parallel to the (001) plane. The molecules within a layer are further linked by π–π stacking interactions between the thiadiazole rings [Cg1⋯Cg4(x, y, z) = 3.636 (3) Å, slippage = 1.283 Å, where Cg1 and Cg4 are the centroids of the rings S1/N3/N4/C1/C2 and S2/N14/N15/C12/C13, respectively]. The layers are linked by van der Waals interactions (Table 2), forming a three-dimensional supramolecular structure (Fig. 5).

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 and Cg6 are the centroids of the S2/N14/N15/C12/C13 and C17–C22 rings, respectively

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N14ⁱ	0.88	2.10	2.974 (6)	172
N1—H1B⋯N4ⁱⁱ	0.88	2.20	3.071 (5)	169
N12—H12A⋯N3ⁱⁱⁱ	0.88	2.06	2.933 (6)	174
N12—H12B⋯N15^iv	0.88	2.24	3.108 (5)	170
C4—H4⋯N2^iv	0.95	2.56	3.363 (6)	142
C15—H15⋯N13ⁱⁱ	0.95	2.46	3.323 (6)	151
C8—H8⋯Cg6^v	0.95	2.98	3.774 (6)	142
C22—H22⋯Cg4ⁱ	0.95	2.95	3.648 (6)	132
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, -y, z]$ ; (iii) x, y+1, z; (iv) $[x-{\script{1\over 2}}, -y+1, z]$ ; (v) $[-x+{\script{1\over 2}}, y+1, z+{\script{1\over 2}}]$ .

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
S1⋯H12B	3.10	$[{1\over 2}]$ + x, 1 − y, z
N2⋯H4	2.56	$[{1\over 2}]$ + x, 1 − y, z
N3⋯H12A	2.06	x, −1 + y, z
H1B⋯S2	3.09	$[{1\over 2}]$ + x, −y, z
H1B⋯N4	2.20	$[{1\over 2}]$ + x, −y, z
C2⋯N14	3.437 (7)	x, y, z
C4⋯H10	3.05	x, −1 + y, z
C7⋯H20	2.91	1 − x, −y, $[{1\over 2}]$ + z
H10⋯H19	2.49	1 − x, 1 − y, $[{1\over 2}]$ + z
H8⋯C18	2.87	$[{1\over 2}]$ − x, 1 + y, $[{1\over 2}]$ + z
H9⋯H21	2.59	$[{1\over 2}]$ − x, 2 + y, $[{1\over 2}]$ + z
N13⋯H15	2.46	− $[{1\over 2}]$ + x, −y, z
H12B⋯N15	2.24	− $[{1\over 2}]$ + x, 1 − y, z
C13⋯H22	2.91	x, 1 + y, z
C19⋯H22	2.94	$[{1\over 2}]$ + x, −1 − y, z

Figure 3
A view of the intermolecular N—H⋯N and C—H⋯N interactions in the crystal structure of the title compound projected along the a axis.

Figure 4
A view of the intermolecular N—H⋯N and C—H⋯N interactions in the crystal structure of the title compound projected along the b axis.

Figure 5
A view of the layer structure formed by intermolecular N—H⋯N, C—H⋯N, C—H⋯π and π–π interactions in the crystal structure of the title compound projected along the b axis.

4. Hirshfeld surface analysis

Crystal Explorer 17 (Turner et al., 2017 ) was used to construct Hirshfeld surfaces for both independent molecules in the asymmetric unit of the title compound. The d_norm mappings for molecule I were performed in the range of −0.5418 to 1.2328 a.u., and for molecule II in the range of −0.5446 to 1.1988 a.u. On the d_norm surfaces, bold red circles show the locations of N—H⋯N interactions. Smaller red spots are caused by C—H⋯N interactions (Fig. 6a,b for molecule I and Fig. 6c,d for molecule II).

Figure 6
Front (a) and back (b) views of the three-dimensional Hirshfeld surface for molecule I. Front (c) and back (d) views of the three-dimensional Hirshfeld surface for molecule II. Some intermolecular N—H⋯N and C—H⋯N interactions are shown as dashed lines.

Fingerprint plots (Fig. 7) reveal that while H⋯H (26.6% for molecule I and 25.3% for molecule II) interactions make the largest contributions to the surface contacts (Table 2), N⋯H/H⋯N (24.1% for I and 24.1% for II) and C⋯H/H⋯C (19.3% for I and 21.0% for II) contacts are also significant. The contributions of other, less noteworthy contacts are listed in Table 3. The environments of molecules I and II are quite similar, as indicated in Table 3.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	molecule I	molecule II
H⋯H	26.6	25.3
N⋯H/H⋯N	24.1	24.1
C⋯H/H⋯C	19.3	21.0
S⋯C/C⋯S	6.7	5.5
O⋯H/H⋯O	6.0	5.5
S⋯H/H⋯S	5.9	6.9
N⋯C/C⋯N	4.5	5.3
O⋯C/C⋯O	2.5	2.6
C⋯C	1.3	0.9
O⋯N/N⋯O	1.1	1.0
N⋯N	1.0	0.9
S⋯N/N⋯S	0.9	0.8
S⋯O/O⋯S	0.1	0.1

Figure 7
The two-dimensional fingerprint plots for molecules I and II of the title compound showing (a) all interactions, and delineated into (b) H⋯H, (c) N⋯H/H⋯N and (d) C⋯H/H⋯C interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

5. Database survey

The only hit related to the title compound found in a search of the Cambridge Structural Database (CSD, Version 5.42; May 2021; Groom et al., 2016 ) was 1-{[3-(thiophen-2-yl)-4,5-dihydro-1,2-oxazol-5-yl]methyl}-1H-indole-2,3-dione (NAQQOO: Rayni et al., 2017 ). In the structure of NAQQOO, the indole ring system is almost planar as expected. The dihedral angle between this plane and that of the thiophene ring is 2.01 (2)°. The mean plane of the isoxazole ring is inclined by 19.78 (14) and 20.83 (12)° to the thiophene and indoline mean planes, respectively. In the crystal, the combination of C—H⋯O hydrogen bonds forms stepped layers two molecules thick, or slabs, which are oriented parallel to ( $[\overline{1}]$ 03). These layers are associated through offset π-stacking interactions, involving inversion-related indole rings in adjacent layers [interplanar distance of 3.479 (1) Å], forming a supramolecular three-dimensional structure.

6. Synthesis and crystallization

5-(5-Phenylisoxazol-3-yl)-1,3,4-thiadiazol-2-amine:

Thiosemicarbazide (1.0 g, 11 mmol) was added at r.t to a solution of 5-phenylisoxazole-3-carbonitrile (1.70 g, 10 mmol) in CF₃CO₂H (10 mL), and the resulting mixture was heated under reflux for 6 h. After cooling, the mixture was poured into water (150 mL) and basified with 25% aqueous ammonia to pH ∼8. The precipitate was filtered off, washed with warm H₂O (3 × 30 mL) and dried under reduced pressure over P₂O₅. The obtained solid product was recrystallized from MeOH giving light-yellow cubic crystals, yield 2.37 g (97%), m.p. = 501–503 K. IR (KBr), ν (cm⁻¹): 3413, 3278, 3147, 3125, 2927, 1615, 1592, 1575, 1508, 1450, 1436, 1417, 1323, 1220, 1140, 1068, 947, 931, 817, 763, 686, 661, 629, 575. ¹H NMR (DMSO-d₆, 500 MHz, 301 K): δ = 7.51–7.58 (m, 4H, 3HAr + 1H-isox), 7.80 (br.s, 2H, NH₂), 7.92–7.98 (m, 2HAr). ¹³C NMR (DMSO-d₆, 125 MHz, 301 K): δ = 98.53 (CH-isox), 126.45 (2CHAr), 129.89 (2CHAr), 131.47 (1CHAr), 126.90, 145.57, 157.67, 170.46, 170.76 (5C). Mass-spectrum, m/z (I_rel, %): 267 [M+Na]⁺ (5), 245 [M+H]⁺ (100). Elemental analysis calculated for C₁₁H₈N₄OS (%): C 54.09, H 3.30, N 22.94, S 13.12; found (%): C 54.21, H 3.11, N 22.99, S 13.18.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All H atoms were positioned geometrically (N—H = 0.88 Å, C—H = 0.95 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(N, C).

Table 4
Experimental details

Crystal data
Chemical formula	C₁₁H₈N₄OS
M_r	244.27
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	11.142 (2), 7.2555 (15), 27.333 (6)
V (Å³)	2209.6 (8)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.24 × 0.18 × 0.02

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.924, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	37296, 6442, 4347
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.125, 1.03
No. of reflections	6442
No. of parameters	307
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.34
Absolute structure	Flack x determined using 1699 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.44 (7)
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2162503

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022003450/yk2168sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022003450/yk2168Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022003450/yk2168Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

5-(5-Phenyl-1,2-oxazol-3-yl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₁₁H₈N₄OS	D_x = 1.469 Mg m⁻³
M_r = 244.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 5781 reflections
a = 11.142 (2) Å	θ = 2.8–28.1°
b = 7.2555 (15) Å	µ = 0.28 mm⁻¹
c = 27.333 (6) Å	T = 100 K
V = 2209.6 (8) Å³	Plate, yellow
Z = 8	0.24 × 0.18 × 0.02 mm
F(000) = 1008

Data collection top

Bruker D8 QUEST PHOTON-III CCD diffractometer	4347 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.110
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 30.0°, θ_min = 2.8°
T_min = 0.924, T_max = 0.985	h = −15→15
37296 measured reflections	k = −10→10
6442 independent reflections	l = −38→38

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + 1.1115P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
6442 reflections	Δρ_max = 0.32 e Å⁻³
307 parameters	Δρ_min = −0.34 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1699 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: difference Fourier map	Absolute structure parameter: 0.44 (7)

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	0.55238 (9)	0.15104 (17)	0.56580 (4)	0.0346 (3)
O1	0.4133 (3)	0.6622 (5)	0.63143 (14)	0.0407 (8)
N1	0.5629 (3)	−0.1735 (6)	0.51880 (17)	0.0411 (11)
H1A	0.5313	−0.2668	0.5028	0.049*
H1B	0.6408	−0.1700	0.5241	0.049*
N2	0.4659 (3)	0.5198 (6)	0.60417 (16)	0.0404 (10)
N3	0.3753 (3)	−0.0298 (6)	0.52886 (16)	0.0368 (10)
N4	0.3268 (3)	0.1278 (6)	0.54882 (15)	0.0363 (9)
C1	0.4931 (4)	−0.0378 (7)	0.53495 (18)	0.0337 (11)
C2	0.4066 (3)	0.2358 (7)	0.56877 (18)	0.0324 (10)
C3	0.3784 (4)	0.4041 (7)	0.59427 (18)	0.0325 (10)
C4	0.2667 (4)	0.4653 (7)	0.61365 (18)	0.0339 (10)
H4	0.1905	0.4077	0.6107	0.041*
C5	0.2934 (4)	0.6234 (7)	0.63716 (19)	0.0353 (11)
C6	0.2228 (4)	0.7554 (7)	0.66463 (18)	0.0381 (11)
C7	0.1161 (4)	0.6999 (7)	0.68654 (19)	0.0400 (11)
H7	0.0917	0.5746	0.6847	0.048*
C8	0.0454 (5)	0.8268 (9)	0.7110 (2)	0.0547 (16)
H8	−0.0272	0.7883	0.7261	0.066*
C9	0.0801 (6)	1.0089 (10)	0.7136 (2)	0.0622 (17)
H9	0.0305	1.0958	0.7299	0.075*
C10	0.1865 (6)	1.0655 (9)	0.6926 (2)	0.0586 (16)
H10	0.2103	1.1910	0.6949	0.070*
C11	0.2591 (5)	0.9399 (7)	0.66806 (19)	0.0435 (12)
H11	0.3325	0.9788	0.6538	0.052*
S2	0.25267 (9)	0.34769 (16)	0.43188 (5)	0.0345 (3)
O12	0.3748 (3)	−0.1645 (5)	0.36528 (14)	0.0414 (8)
N12	0.2466 (3)	0.6713 (6)	0.47918 (16)	0.0401 (10)
H12A	0.2801	0.7631	0.4952	0.048*
H12B	0.1686	0.6711	0.4740	0.048*
N13	0.3275 (3)	−0.0167 (6)	0.39175 (17)	0.0406 (10)
N14	0.4322 (3)	0.5220 (6)	0.46910 (15)	0.0354 (9)
N15	0.4782 (3)	0.3622 (5)	0.44954 (15)	0.0336 (9)
C12	0.3137 (4)	0.5330 (7)	0.46289 (18)	0.0325 (11)
C13	0.3977 (3)	0.2571 (7)	0.42917 (19)	0.0324 (10)
C14	0.4201 (4)	0.0858 (7)	0.40348 (19)	0.0339 (11)
C15	0.5296 (4)	0.0103 (7)	0.38637 (18)	0.0355 (11)
H15	0.6085	0.0576	0.3907	0.043*
C16	0.4959 (4)	−0.1445 (7)	0.36254 (19)	0.0348 (10)
C17	0.5587 (4)	−0.2878 (7)	0.33530 (18)	0.0354 (11)
C18	0.6693 (4)	−0.2494 (8)	0.31302 (18)	0.0403 (12)
H18	0.7024	−0.1289	0.3145	0.048*
C19	0.7299 (5)	−0.3898 (8)	0.2886 (2)	0.0487 (14)
H19	0.8046	−0.3646	0.2733	0.058*
C20	0.6826 (5)	−0.5652 (9)	0.2866 (2)	0.0519 (14)
H20	0.7252	−0.6607	0.2704	0.062*
C21	0.5732 (5)	−0.6019 (8)	0.3082 (2)	0.0492 (14)
H21	0.5400	−0.7223	0.3063	0.059*
C22	0.5121 (5)	−0.4653 (7)	0.3324 (2)	0.0422 (12)
H22	0.4372	−0.4923	0.3474	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0126 (4)	0.0464 (6)	0.0447 (7)	−0.0005 (4)	−0.0026 (4)	−0.0051 (6)
O1	0.0207 (14)	0.047 (2)	0.055 (2)	−0.0023 (14)	0.0010 (14)	−0.0061 (18)
N1	0.0154 (16)	0.047 (3)	0.061 (3)	0.0009 (17)	−0.0043 (17)	−0.011 (2)
N2	0.0187 (18)	0.049 (3)	0.053 (3)	−0.0012 (17)	0.0002 (17)	−0.006 (2)
N3	0.0159 (17)	0.047 (2)	0.048 (3)	−0.0013 (16)	−0.0018 (16)	−0.002 (2)
N4	0.0162 (17)	0.050 (3)	0.043 (2)	0.0009 (17)	−0.0030 (15)	0.0001 (19)
C1	0.0166 (19)	0.047 (3)	0.037 (3)	−0.0025 (18)	0.0005 (18)	0.000 (2)
C2	0.0130 (16)	0.048 (3)	0.036 (3)	0.0006 (17)	−0.0018 (18)	0.003 (2)
C3	0.0170 (19)	0.044 (3)	0.036 (3)	−0.0025 (18)	−0.0032 (17)	0.003 (2)
C4	0.0175 (19)	0.045 (3)	0.039 (3)	−0.0010 (19)	−0.0010 (18)	0.001 (2)
C5	0.0191 (19)	0.050 (3)	0.037 (3)	−0.0005 (18)	−0.0018 (19)	0.006 (2)
C6	0.031 (2)	0.049 (3)	0.034 (3)	0.006 (2)	−0.0073 (19)	0.000 (2)
C7	0.028 (2)	0.059 (3)	0.033 (3)	0.008 (2)	−0.005 (2)	−0.001 (2)
C8	0.038 (3)	0.086 (5)	0.040 (3)	0.012 (3)	0.002 (2)	−0.004 (3)
C9	0.062 (4)	0.071 (4)	0.053 (4)	0.020 (3)	0.003 (3)	−0.021 (3)
C10	0.064 (4)	0.056 (4)	0.056 (4)	0.005 (3)	−0.002 (3)	−0.012 (3)
C11	0.044 (3)	0.048 (3)	0.039 (3)	0.003 (2)	−0.003 (2)	−0.003 (2)
S2	0.0129 (4)	0.0473 (6)	0.0433 (6)	−0.0003 (5)	−0.0025 (4)	−0.0049 (6)
O12	0.0193 (15)	0.049 (2)	0.056 (2)	−0.0022 (14)	−0.0014 (15)	−0.0103 (18)
N12	0.0158 (17)	0.051 (3)	0.053 (3)	0.0013 (17)	−0.0033 (16)	−0.013 (2)
N13	0.0206 (19)	0.048 (3)	0.054 (3)	0.0026 (18)	−0.0004 (18)	−0.007 (2)
N14	0.0158 (17)	0.047 (2)	0.044 (2)	−0.0001 (15)	−0.0025 (15)	−0.0051 (19)
N15	0.0155 (16)	0.044 (2)	0.041 (2)	−0.0003 (15)	−0.0010 (14)	−0.0016 (18)
C12	0.0150 (19)	0.043 (3)	0.039 (3)	−0.0015 (18)	−0.0035 (17)	0.000 (2)
C13	0.0147 (16)	0.044 (3)	0.039 (3)	−0.0014 (17)	−0.0005 (18)	0.005 (2)
C14	0.0138 (18)	0.046 (3)	0.041 (3)	0.0009 (18)	−0.0021 (17)	0.004 (2)
C15	0.0135 (18)	0.051 (3)	0.042 (3)	0.0038 (19)	−0.0004 (18)	0.002 (2)
C16	0.0163 (19)	0.051 (3)	0.037 (2)	0.0032 (19)	−0.0007 (17)	0.005 (2)
C17	0.025 (2)	0.048 (3)	0.033 (3)	0.003 (2)	−0.0036 (19)	0.004 (2)
C18	0.021 (2)	0.056 (3)	0.044 (3)	0.005 (2)	−0.0004 (18)	0.004 (2)
C19	0.033 (3)	0.070 (4)	0.042 (3)	0.014 (2)	0.008 (2)	0.009 (3)
C20	0.051 (3)	0.061 (4)	0.044 (3)	0.018 (3)	0.003 (3)	−0.002 (3)
C21	0.052 (4)	0.050 (3)	0.045 (3)	0.002 (3)	0.003 (3)	0.000 (3)
C22	0.035 (3)	0.052 (3)	0.039 (3)	0.001 (2)	−0.001 (2)	0.000 (2)

Geometric parameters (Å, º) top

S1—C1	1.739 (5)	S2—C12	1.729 (5)
S1—C2	1.739 (4)	S2—C13	1.746 (4)
O1—C5	1.374 (5)	O12—C16	1.359 (5)
O1—N2	1.402 (5)	O12—N13	1.398 (5)
N1—C1	1.330 (6)	N12—C12	1.328 (6)
N1—H1A	0.8800	N12—H12A	0.8800
N1—H1B	0.8800	N12—H12B	0.8800
N2—C3	1.315 (6)	N13—C14	1.312 (6)
N3—C1	1.324 (5)	N14—C12	1.334 (5)
N3—N4	1.377 (6)	N14—N15	1.376 (5)
N4—C2	1.304 (6)	N15—C13	1.302 (6)
C2—C3	1.441 (7)	C13—C14	1.449 (7)
C3—C4	1.424 (6)	C14—C15	1.417 (6)
C4—C5	1.348 (7)	C15—C16	1.352 (7)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.449 (7)	C16—C17	1.458 (7)
C6—C7	1.391 (7)	C17—C22	1.391 (7)
C6—C11	1.402 (7)	C17—C18	1.402 (7)
C7—C8	1.384 (7)	C18—C19	1.393 (7)
C7—H7	0.9500	C18—H18	0.9500
C8—C9	1.378 (9)	C19—C20	1.379 (8)
C8—H8	0.9500	C19—H19	0.9500
C9—C10	1.379 (9)	C20—C21	1.380 (8)
C9—H9	0.9500	C20—H20	0.9500
C10—C11	1.391 (8)	C21—C22	1.373 (7)
C10—H10	0.9500	C21—H21	0.9500
C11—H11	0.9500	C22—H22	0.9500

C1—S1—C2	86.9 (2)	C12—S2—C13	87.1 (2)
C5—O1—N2	108.4 (3)	C16—O12—N13	108.7 (4)
C1—N1—H1A	120.0	C12—N12—H12A	120.0
C1—N1—H1B	120.0	C12—N12—H12B	120.0
H1A—N1—H1B	120.0	H12A—N12—H12B	120.0
C3—N2—O1	105.7 (4)	C14—N13—O12	105.3 (4)
C1—N3—N4	112.0 (4)	C12—N14—N15	111.7 (4)
C2—N4—N3	113.4 (4)	C13—N15—N14	113.8 (4)
N3—C1—N1	124.7 (4)	N12—C12—N14	124.0 (4)
N3—C1—S1	113.8 (4)	N12—C12—S2	122.1 (3)
N1—C1—S1	121.5 (3)	N14—C12—S2	113.9 (4)
N4—C2—C3	124.3 (4)	N15—C13—C14	126.2 (4)
N4—C2—S1	113.9 (4)	N15—C13—S2	113.5 (4)
C3—C2—S1	121.7 (3)	C14—C13—S2	120.2 (3)
N2—C3—C4	111.9 (4)	N13—C14—C15	112.2 (5)
N2—C3—C2	118.6 (4)	N13—C14—C13	117.9 (4)
C4—C3—C2	129.4 (4)	C15—C14—C13	129.8 (4)
C5—C4—C3	104.4 (4)	C16—C15—C14	103.9 (4)
C5—C4—H4	127.8	C16—C15—H15	128.0
C3—C4—H4	127.8	C14—C15—H15	128.0
C4—C5—O1	109.6 (4)	C15—C16—O12	109.8 (4)
C4—C5—C6	133.6 (4)	C15—C16—C17	134.9 (4)
O1—C5—C6	116.8 (4)	O12—C16—C17	115.4 (4)
C7—C6—C11	119.6 (5)	C22—C17—C18	119.2 (5)
C7—C6—C5	119.7 (5)	C22—C17—C16	120.6 (5)
C11—C6—C5	120.6 (5)	C18—C17—C16	120.1 (5)
C8—C7—C6	120.1 (5)	C19—C18—C17	119.2 (5)
C8—C7—H7	119.9	C19—C18—H18	120.4
C6—C7—H7	119.9	C17—C18—H18	120.4
C9—C8—C7	120.2 (6)	C20—C19—C18	120.6 (5)
C9—C8—H8	119.9	C20—C19—H19	119.7
C7—C8—H8	119.9	C18—C19—H19	119.7
C8—C9—C10	120.4 (6)	C19—C20—C21	119.9 (5)
C8—C9—H9	119.8	C19—C20—H20	120.0
C10—C9—H9	119.8	C21—C20—H20	120.0
C9—C10—C11	120.3 (6)	C22—C21—C20	120.4 (6)
C9—C10—H10	119.8	C22—C21—H21	119.8
C11—C10—H10	119.8	C20—C21—H21	119.8
C10—C11—C6	119.4 (5)	C21—C22—C17	120.7 (5)
C10—C11—H11	120.3	C21—C22—H22	119.7
C6—C11—H11	120.3	C17—C22—H22	119.7

C5—O1—N2—C3	0.5 (5)	C16—O12—N13—C14	0.4 (5)
C1—N3—N4—C2	0.8 (6)	C12—N14—N15—C13	0.3 (6)
N4—N3—C1—N1	−179.2 (5)	N15—N14—C12—N12	178.6 (5)
N4—N3—C1—S1	−0.2 (5)	N15—N14—C12—S2	−0.7 (5)
C2—S1—C1—N3	−0.2 (4)	C13—S2—C12—N12	−178.6 (5)
C2—S1—C1—N1	178.7 (5)	C13—S2—C12—N14	0.7 (4)
N3—N4—C2—C3	−176.7 (5)	N14—N15—C13—C14	176.6 (5)
N3—N4—C2—S1	−1.0 (6)	N14—N15—C13—S2	0.3 (6)
C1—S1—C2—N4	0.7 (4)	C12—S2—C13—N15	−0.5 (4)
C1—S1—C2—C3	176.5 (4)	C12—S2—C13—C14	−177.1 (4)
O1—N2—C3—C4	0.7 (6)	O12—N13—C14—C15	−0.9 (6)
O1—N2—C3—C2	−176.3 (4)	O12—N13—C14—C13	176.6 (4)
N4—C2—C3—N2	−166.4 (5)	N15—C13—C14—N13	169.7 (5)
S1—C2—C3—N2	18.2 (7)	S2—C13—C14—N13	−14.2 (7)
N4—C2—C3—C4	17.1 (9)	N15—C13—C14—C15	−13.3 (9)
S1—C2—C3—C4	−158.3 (4)	S2—C13—C14—C15	162.9 (4)
N2—C3—C4—C5	−1.7 (6)	N13—C14—C15—C16	1.1 (6)
C2—C3—C4—C5	174.9 (5)	C13—C14—C15—C16	−176.1 (5)
C3—C4—C5—O1	2.0 (6)	C14—C15—C16—O12	−0.7 (6)
C3—C4—C5—C6	−180.0 (5)	C14—C15—C16—C17	178.6 (6)
N2—O1—C5—C4	−1.7 (6)	N13—O12—C16—C15	0.2 (6)
N2—O1—C5—C6	179.9 (4)	N13—O12—C16—C17	−179.2 (4)
C4—C5—C6—C7	24.7 (9)	C15—C16—C17—C22	152.5 (6)
O1—C5—C6—C7	−157.4 (4)	O12—C16—C17—C22	−28.2 (7)
C4—C5—C6—C11	−153.3 (6)	C15—C16—C17—C18	−25.4 (9)
O1—C5—C6—C11	24.5 (7)	O12—C16—C17—C18	154.0 (5)
C11—C6—C7—C8	0.9 (8)	C22—C17—C18—C19	−0.2 (7)
C5—C6—C7—C8	−177.2 (5)	C16—C17—C18—C19	177.7 (5)
C6—C7—C8—C9	0.3 (8)	C17—C18—C19—C20	−0.4 (8)
C7—C8—C9—C10	−1.2 (10)	C18—C19—C20—C21	1.0 (9)
C8—C9—C10—C11	0.8 (10)	C19—C20—C21—C22	−1.1 (9)
C9—C10—C11—C6	0.4 (9)	C20—C21—C22—C17	0.5 (9)
C7—C6—C11—C10	−1.2 (8)	C18—C17—C22—C21	0.1 (8)
C5—C6—C11—C10	176.8 (5)	C16—C17—C22—C21	−177.8 (5)

Hydrogen-bond geometry (Å, º) top

Cg4 and Cg6 are the centroids of the S2/N14/N15/C12/C13 and C17–C22 rings, respectively

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N14ⁱ	0.88	2.10	2.974 (6)	172
N1—H1B···N4ⁱⁱ	0.88	2.20	3.071 (5)	169
N12—H12A···N3ⁱⁱⁱ	0.88	2.06	2.933 (6)	174
N12—H12B···N15^iv	0.88	2.24	3.108 (5)	170
C4—H4···N2^iv	0.95	2.56	3.363 (6)	142
C15—H15···N13ⁱⁱ	0.95	2.46	3.323 (6)	151
C8—H8···Cg6^v	0.95	2.98	3.774 (6)	142
C22—H22···Cg4ⁱ	0.95	2.95	3.648 (6)	132

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

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
S1···H12B	3.10	1/2 + x, 1 - y, z
N2···H4	2.56	1/2 + x, 1 - y, z
N3···H12A	2.06	x, -1 + y, z
H1B···S2	3.09	1/2 + x, -y, z
H1B···N4	2.20	1/2 + x, -y, z
C2···N14	3.437	x, y, z
C4···H10	3.05	x, -1 + y, z
C7···H20	2.91	1 - x, -y, 1/2 + z
H10···H19	2.49	1 - x, 1 - y, 1/2 + z
H8···C18	2.87	1/2 - x, 1 + y, 1/2 + z
H9···H21	2.59	1/2 - x, 2 + y, 1/2 + z
N13···H15	2.46	-1/2 + x, -y, z
H12B···N15	2.24	-1/2 + x, 1 - y, z
C13···H22	2.91	x, 1 + y, z
C19···H22	2.94	1/2 + x, -1 - y, z

Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound top

Contact	molecule I	molecule II
H···H	26.6	25.3
N···H/H···N	24.1	24.1
C···H/H···C	19.3	21.0
S···C/C···S	6.7	5.5
O···H/H···O	6.0	5.5
S···H/H···S	5.9	6.9
N···C/C···N	4.5	5.3
O···C/C···O	2.5	2.6
C···C	1.3	0.9
O···N/N···O	1.1	1.0
N···N	1.0	0.9
S···N/N···S	0.9	0.8
S···O/O···S	0.1	0.1

Acknowledgements

The authors' contributions are as follows: Conceptualization, EVN, MA and SM; synthesis, EVN, EKP, SKP and EAA; X-ray analysis, STÇ, VNK and MA; writing (review and editing of the manuscript), EVN, STÇ, MA and SM; funding acquisition, EVN, SKP, EAA and SM; supervision, MA, SKP and SM.

Funding information

EVN is grateful to the Russian Foundation for Basic Research (RFBR) (award No. 19–53-04002, Bel_mol_a) and the Belarusian Republican Foundation for Fundamental Research (BRFFR) (award No. X20PM-056) for financial support of this research.

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