Crystal structure and Hirshfeld surface analysis of 2-amino-5-{(1E)-1-[(carbamo­thioyl­amino)­imino]eth­yl}-4-methyl-1,3-thia­zol-3-ium chloride monohydrate

Huseynov, E.Z.; Akkurt, M.; Brito, I.; Bhattarai, A.; Naghiyev, F.N.; Asadov, K.A.; Maharramov, A.M.

doi:10.1107/S2056989023007090

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ISSN: 2056-9890

Volume 79| Part 9| September 2023| Pages 808-812

https://doi.org/10.1107/S2056989023007090

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Crystal structure and Hirshfeld surface analysis of 2-amino-5-{(1E)-1-[(carbamothioylamino)imino]ethyl}-4-methyl-1,3-thiazol-3-ium chloride monohydrate

Elnur Z. Huseynov,^a Mehmet Akkurt,^b Ivan Brito,^c Ajaya Bhattarai,^d ^* Farid N. Naghiyev,^a Khammed A. Asadov ^a and Abel M. Maharramov ^a

^aDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, Az, 1148 Baku, Azerbaijan, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, ^cDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Avenida Angamos 601, Casilla 170, Antofagasta 1240000, Chile, and ^dDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by M. Weil, Vienna University of Technology, Austria (Received 2 August 2023; accepted 11 August 2023; online 17 August 2023)

In the hydrated title salt, C₇H₁₂N₅S₂⁺·Cl⁻·H₂O, the asymmetric unit comprises one 2-amino-5-{(1E)-1-[(carbamothioylamino)imino]ethyl}-4-methyl-1,3-thiazol-3-ium cation, one chloride anion and one water molecule of crystallization. The cation is nearly flat (r.m.s. deviation of non-H atoms is 0.0814 Å), with the largest deviation of 0.1484 (14) Å observed for one of the methyl C atoms. In the crystal, the cations are linked by O—H⋯Cl, N—H⋯Cl, N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds, forming a tri-periodic network. The most important contributions to the crystal packing are from H⋯H (35.4%), S⋯H/H⋯S (24.4%), N⋯H/H⋯N (8.7%), Cl⋯H/H⋯Cl (8.2%) and C⋯H/H⋯C (7.7%) interactions.

Keywords: crystal structure; 1,3-thiazol-3-ium; hydrogen bonds; hydrogen-bonded network; Hirshfeld surface analysis.

CCDC reference: 2288159

1. Chemical context

Heterocyclic systems account for many important organic compounds (Maharramov et al., 2011b ; Abdelhamid et al., 2014 ). In particular, five- and six-membered heterocycles are applied in different branches of chemistry, including sustainable chemistry (Montes et al., 2018 ), drug design and development (Khalilov et al., 2021 ; Tas et al., 2023 ) or material science (Yin et al., 2020 ). The thiazole core is one of the most common five-membered heteroaromatic ring systems (Yadigarov et al., 2009 ; Khalilov, 2021 ). Thiazoles have potent biological applications and represent an essential core scaffold present in many natural (thiamine, penicillin) and synthetic medicinally important compounds (Chhabria et al., 2016 ), such as sulfazole, ritonavir, abafungin, fanetizole, meloxicam, fentiazac, nizatidine and thiamethoxam (Fig. 1). A variety of thiazole derivatives are also used as target products as well as synthetic intermediates (Maharramov et al., 2011a ; Kekeçmuhammed et al., 2022 ).

Figure 1
Chemical diagrams of some thiazole-containing marketed drugs with trade names.

In a continuation of our structural investigations of heterocyclic systems associated with biological activities (Akkurt et al., 2018 ; Askerov et al., 2020 ; Karimli et al., 2023 ), we report here the crystal structure and Hirshfeld surface analysis of the hydrated title salt, C₇H₁₂N₅S₂⁺·Cl⁻·H₂O, (I).

2. Structural commentary

The asymmetric unit of (I) (Fig. 2) comprises one 2-amino-5-{(1E)-1-[(carbamothioylamino)imino]ethyl}-4-methyl-1,3-thiazol-3-ium cation, C₇H₁₂N₅S₂⁺, one chloride anion and one water molecule of crystallization. In the 1,3-thiazol-3-ium ring, as expected, the C1—N2 distance of 1.3309 (16) Å indicates double-bond character, while the C2—N2 distance of 1.3885 (14) Å has more single-bond character.

Figure 2
The molecular structure of (I)

, showing the atom labeling and displacement ellipsoids drawn at the 50% probability level.

In the amino-N′-[(1Z)-ethylidene]ethanethiohydrazide group, the S2—C7—N4—N3, N5—C7—N4—N3, C7—N4—N3—C5 and N4—N3—C5—C6 torsion angles are 178.17 (8), −0.63 (16), 174.48 (10) and 0.16 (18)°, respectively. The title compound shows bond lengths and angles that are typical and are in agreement with those reported for the related compounds discussed in the Database survey section.

The cation is nearly flat (r.m.s. deviation of the 14 non-H atoms is 0.0814 Å), with the largest deviations observed for C6 [0.1484 (14) Å], N1 [0.1357 (10) Å], and S2 [0.1399 (6) Å].

3. Supramolecular features and Hirshfeld surface analysis

In the crystal of (I), the cations are linked by O—H⋯Cl, N—H⋯Cl, N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds (Table 1), forming a tri-periodic network (Figs. 3–5 ). Significant C—H⋯π or π–π interactions are not developed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—HW1⋯Cl1ⁱ	0.79 (3)	2.45 (3)	3.2298 (13)	171 (3)
N2—H2⋯Cl1ⁱⁱ	0.853 (18)	2.277 (18)	3.0812 (11)	157.2 (15)
OW1—HW2⋯Cl1	0.71 (3)	2.50 (3)	3.2111 (14)	178 (3)
N1—H11⋯Cl1ⁱⁱⁱ	0.78 (3)	2.81 (2)	3.2398 (15)	117.0 (18)
N1—H12⋯OW1^iv	0.87 (2)	1.97 (2)	2.8354 (19)	174 (2)
N4—H41⋯S2^v	0.943 (16)	2.686 (16)	3.6223 (11)	172.0 (14)
N5—H51⋯Cl1^vi	0.81 (2)	2.54 (2)	3.3243 (13)	164.9 (18)
N5—H52⋯OW1^vii	0.80 (2)	2.326 (19)	2.9899 (17)	141.2 (19)
C6—H6C⋯S2^v	0.96	2.67	3.4923 (15)	143
Symmetry codes: (i) ; (ii) x+1, y, z; (iii) ; (iv) ; (v) ; (vi) ; (vii) x, y+1, z.

Figure 3
View of the packing of (I)

along the a axis with the O—H⋯Cl, N—H⋯Cl, N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 4
View of the same interactions as in Fig. 2

along the b axis.

Figure 5
View of the same interactions as in Fig. 2

along the c axis.

In order to visualize and quantify intermolecular interactions (Table 2) in (I), a Hirshfeld surface analysis was performed using Crystal Explorer 17.5 (Spackman et al., 2021 ), which was also used for generation of the associated two-dimensional fingerprint plots. The Hirshfeld surface mapped over d_norm shows the intermolecular contacts as red-colored spots, which indicate the O—H⋯Cl, N—H⋯Cl, N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds (Fig. 6).

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

Contact	Distance	Symmetry code
H52⋯OW1	2.33	x, 1 + y, z
C1⋯N5	3.37	1 + x, y, z
C7⋯H4A	2.83	−1 + x, 1 + y, z
H6C⋯S2	2.67	−x, 2 − y, −z
H4C⋯S2	3.08	1 − x, 2 − y, −z
H2⋯Cl1	2.28	1 + x, y, z
H11⋯Cl1	2.81	2 − x, 1 − y, 1 − z
H12⋯OW1	1.97	1 − x, 1 − y, 1 − z
N1⋯N1	3.27	2 − x, 1 − y, 1 − z
H51⋯Cl1	2.54	−1 + x, 1 + y, z
C6⋯C4	3.55	2 − x, 1 − y, −z
Cl1⋯HW2	2.50	x, y, z
Cl1⋯HW1	2.45	1 − x, −y, 1 − z

Figure 6
(a) Front and (b) back sides of the three-dimensional Hirshfeld surface of (I)

mapped over d_norm.

The two-dimensional fingerprint plots of the most abundant contacts are presented in Fig. 7. H⋯H (35.4%) and S⋯H/H⋯S (24.4%) contacts are responsible for the largest contributions to the Hirshfeld surface. Besides these contacts, N⋯H/H⋯N (8.7%), Cl⋯H/H⋯Cl (8.2%) and C⋯H/H⋯C (7.7%) interactions contribute significantly to the total Hirshfeld surface. The contributions of further contacts are only minor and amount to C⋯H/H⋯C (4.5%), S⋯C/C⋯S (2.4%), N⋯C/C⋯N (2.1%), N⋯N (1.9%), C⋯C (1.6%), S⋯N/N⋯S (1.3%), Cl⋯S/S⋯Cl (0.6%), Cl⋯C/C⋯Cl (0.6%), S⋯S (0.4%), N⋯O/O⋯N (%0.1) and S⋯O/O⋯S (0.1%).

Figure 7
The two-dimensional fingerprint plots of (I)

, showing (a) all interactions, and delineated into (b) H⋯H, (c) S⋯H/H⋯S, (d) N⋯H/H⋯N, (e) Cl⋯H/H⋯Cl and (f) C⋯H/H⋯C interactions. [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

4. Database survey

A search of the Cambridge Crystallographic Database (updated 20 March 2023; Groom et al., 2016 ) using the 1,3-thiazol-3-ium moiety as the search fragment revealed four closely related compounds: 2-anilino-3-(2-hydroxypropyl)-4-methyl-1,3-thiazol-3-ium chloride (II) (Mohamed et al., 2012 ), 2-amino-5-butyl-4-methyl-1,3-thiazol-3-ium nitrate (III) (Zarychta et al., 2003 ), 2-(2-thioxo-1,3-thiazolidin-3-yl)-4,5-dihydro-l,3-thiazol-l-ium chloride (IV) (Raper et al., 1996 ) and 2-ureido-1,3-thiazol-3-ium dihydrogen phosphate (V) (Gubina et al., 2011 ).

In the crystal of (II), molecules are linked by O—H⋯Cl and N—H⋯Cl hydrogen bonds, forming zigzag chains along [001]. There is also a C—H⋯Cl interaction present. The crystal structure of (III) comprises a substituted thiazolium ring that is connected to a nitrate ion via N—H⋯O hydrogen-bonding interactions. In the crystal of (IV), the molecular packing is determined by interionic N—H⋯Cl contacts. In the crystal of (V), the molecules of substituted urea are connected by O—H⋯O hydrogen bonds into sheets. In turn, these sheets are connected to each other via N—H⋯O hydrogen bonds with hydrogen phosphate anions, forming a tri-periodic network.

5. Synthesis and crystallization

The title compound was synthesized using a reported procedure (Gomha et al., 2016 ). Colorless crystals were obtained upon recrystallization from an ethanol/water (3:1 v:v) solution at room temperature

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms of the methyl groups were positioned geometrically and refined as riding with C—H = 0.96 Å, with U_iso(H) = 1.5U_eq(C). The H atoms attached to the N atom and the H atoms of the water molecule were found in a difference-Fourier map. Their positional parameters were refined freely while setting U_iso(H) = 1.2U_eq(N) and 1.5U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	C₇H₁₂N₅S₂⁺·Cl⁻·H₂O
M_r	283.80
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	6.3279 (4), 7.7816 (6), 14.1342 (10)
α, β, γ (°)	77.191 (3), 83.660 (3), 67.860 (2)
V (Å³)	628.35 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.62
Crystal size (mm)	0.04 × 0.03 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ).
T_min, T_max	0.570, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	34019, 6058, 4589
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.833

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.115, 1.05
No. of reflections	6058
No. of parameters	171
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.29
Computer programs: APEX2 (Bruker, 2016 ), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2288159

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007090/wm5691sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007090/wm5691Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023007090/wm5691Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); 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).

2-Amino-5-{(1E)-1-[(carbamothioylamino)imino]ethyl}-4-methyl-1,3-thiazol-3-ium chloride monohydrate top

Crystal data top

C₇H₁₂N₅S₂⁺·Cl⁻·H₂O	Z = 2
M_r = 283.80	F(000) = 296
Triclinic, P1	D_x = 1.500 Mg m⁻³
a = 6.3279 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7816 (6) Å	Cell parameters from 9921 reflections
c = 14.1342 (10) Å	θ = 3.0–36.3°
α = 77.191 (3)°	µ = 0.62 mm⁻¹
β = 83.660 (3)°	T = 293 K
γ = 67.860 (2)°	Prism, colourless
V = 628.35 (8) Å³	0.04 × 0.03 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	4589 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.053
Absorption correction: multi-scan (SADABS; Krause et al., 2015).	θ_max = 36.3°, θ_min = 3.0°
T_min = 0.570, T_max = 0.747	h = −10→10
34019 measured reflections	k = −12→12
6058 independent reflections	l = −23→21

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0567P)² + 0.0995P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
6058 reflections	Δρ_max = 0.50 e Å⁻³
171 parameters	Δρ_min = −0.29 e Å⁻³

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	1.00052 (18)	0.66580 (16)	0.37114 (8)	0.0336 (2)
C2	1.00425 (17)	0.58328 (15)	0.22387 (8)	0.03023 (18)
C3	0.78120 (16)	0.69558 (14)	0.23070 (7)	0.02811 (17)
C4	1.1391 (2)	0.4821 (2)	0.14588 (10)	0.0429 (3)
H4A	1.053893	0.420248	0.123677	0.064*
H4B	1.281001	0.389685	0.171192	0.064*
H4C	1.169126	0.571545	0.092670	0.064*
C5	0.59592 (16)	0.76248 (15)	0.16319 (7)	0.02893 (17)
C6	0.6438 (2)	0.7189 (2)	0.06335 (10)	0.0474 (3)
H6A	0.648883	0.593175	0.065682	0.071*
H6B	0.788013	0.727617	0.039126	0.071*
H6C	0.525339	0.807944	0.021177	0.071*
C7	0.01732 (16)	1.05991 (15)	0.17123 (7)	0.02918 (17)
N1	1.0867 (2)	0.6736 (2)	0.45014 (10)	0.0471 (3)
H11	1.215 (4)	0.611 (3)	0.4604 (14)	0.057*
H12	0.992 (4)	0.756 (3)	0.4827 (15)	0.057*
N2	1.12182 (15)	0.56820 (14)	0.30449 (7)	0.03419 (18)
H2	1.261 (3)	0.496 (2)	0.3136 (12)	0.041*
N3	0.40159 (14)	0.86322 (14)	0.19705 (7)	0.03073 (16)
N4	0.21575 (15)	0.94127 (14)	0.13782 (7)	0.03273 (18)
H41	0.214 (3)	0.927 (2)	0.0734 (12)	0.039*
N5	0.01285 (18)	1.09259 (17)	0.25930 (8)	0.0395 (2)
H51	−0.101 (3)	1.160 (3)	0.2836 (13)	0.047*
H52	0.117 (3)	1.046 (3)	0.2953 (13)	0.047*
S1	0.71982 (4)	0.78020 (4)	0.33975 (2)	0.03514 (7)
S2	−0.21036 (5)	1.16255 (5)	0.09918 (2)	0.03939 (8)
Cl1	0.57747 (5)	0.30475 (5)	0.39936 (2)	0.04264 (8)
OW1	0.23501 (19)	0.07771 (18)	0.43851 (9)	0.0517 (3)
HW1	0.288 (4)	−0.009 (4)	0.4806 (19)	0.078*
HW2	0.308 (4)	0.131 (4)	0.4302 (19)	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0290 (4)	0.0352 (5)	0.0351 (5)	−0.0092 (4)	−0.0118 (4)	−0.0030 (4)
C2	0.0241 (4)	0.0307 (4)	0.0325 (4)	−0.0064 (3)	−0.0040 (3)	−0.0042 (3)
C3	0.0230 (4)	0.0313 (4)	0.0283 (4)	−0.0065 (3)	−0.0052 (3)	−0.0062 (3)
C4	0.0341 (5)	0.0456 (6)	0.0429 (6)	−0.0052 (5)	0.0031 (4)	−0.0152 (5)
C5	0.0240 (4)	0.0324 (4)	0.0296 (4)	−0.0081 (3)	−0.0065 (3)	−0.0057 (3)
C6	0.0341 (5)	0.0638 (8)	0.0390 (6)	−0.0028 (5)	−0.0082 (4)	−0.0231 (6)
C7	0.0230 (4)	0.0327 (4)	0.0301 (4)	−0.0080 (3)	−0.0063 (3)	−0.0037 (3)
N1	0.0405 (5)	0.0552 (7)	0.0440 (6)	−0.0094 (5)	−0.0204 (4)	−0.0116 (5)
N2	0.0236 (3)	0.0361 (4)	0.0378 (4)	−0.0047 (3)	−0.0092 (3)	−0.0043 (3)
N3	0.0225 (3)	0.0370 (4)	0.0303 (4)	−0.0071 (3)	−0.0071 (3)	−0.0054 (3)
N4	0.0236 (3)	0.0403 (5)	0.0309 (4)	−0.0050 (3)	−0.0076 (3)	−0.0086 (3)
N5	0.0290 (4)	0.0525 (6)	0.0316 (4)	−0.0055 (4)	−0.0053 (3)	−0.0121 (4)
S1	0.02593 (11)	0.04268 (15)	0.03359 (13)	−0.00389 (10)	−0.00727 (9)	−0.01324 (11)
S2	0.02756 (12)	0.04546 (16)	0.03856 (14)	−0.00214 (10)	−0.01341 (10)	−0.00894 (12)
Cl1	0.02891 (12)	0.04757 (16)	0.04456 (16)	−0.00184 (10)	−0.01143 (10)	−0.01183 (12)
OW1	0.0426 (5)	0.0549 (6)	0.0542 (6)	−0.0121 (4)	−0.0169 (4)	−0.0060 (5)

Geometric parameters (Å, º) top

C1—N1	1.3181 (16)	C6—H6B	0.9600
C1—N2	1.3309 (16)	C6—H6C	0.9600
C1—S1	1.7180 (11)	C7—N5	1.3198 (15)
C2—C3	1.3575 (13)	C7—N4	1.3567 (14)
C2—N2	1.3885 (14)	C7—S2	1.6872 (10)
C2—C4	1.4945 (16)	N1—H11	0.79 (2)
C3—C5	1.4570 (14)	N1—H12	0.87 (2)
C3—S1	1.7565 (10)	N2—H2	0.854 (18)
C4—H4A	0.9600	N3—N4	1.3806 (12)
C4—H4B	0.9600	N4—H41	0.943 (17)
C4—H4C	0.9600	N5—H51	0.81 (2)
C5—N3	1.2906 (13)	N5—H52	0.80 (2)
C5—C6	1.4961 (16)	OW1—HW1	0.78 (3)
C6—H6A	0.9600	OW1—HW2	0.71 (3)

N1—C1—N2	124.00 (11)	C5—C6—H6C	109.5
N1—C1—S1	124.99 (10)	H6A—C6—H6C	109.5
N2—C1—S1	111.01 (8)	H6B—C6—H6C	109.5
C3—C2—N2	111.36 (9)	N5—C7—N4	117.81 (9)
C3—C2—C4	131.66 (10)	N5—C7—S2	122.67 (8)
N2—C2—C4	116.95 (9)	N4—C7—S2	119.51 (8)
C2—C3—C5	131.75 (10)	C1—N1—H11	118.0 (15)
C2—C3—S1	111.21 (8)	C1—N1—H12	113.9 (14)
C5—C3—S1	116.95 (7)	H11—N1—H12	127.9 (19)
C2—C4—H4A	109.5	C1—N2—C2	115.94 (9)
C2—C4—H4B	109.5	C1—N2—H2	120.9 (11)
H4A—C4—H4B	109.5	C2—N2—H2	123.1 (11)
C2—C4—H4C	109.5	C5—N3—N4	118.97 (9)
H4A—C4—H4C	109.5	C7—N4—N3	118.45 (9)
H4B—C4—H4C	109.5	C7—N4—H41	115.1 (10)
N3—C5—C3	113.92 (9)	N3—N4—H41	126.3 (10)
N3—C5—C6	126.22 (10)	C7—N5—H51	122.4 (14)
C3—C5—C6	119.81 (9)	C7—N5—H52	125.2 (13)
C5—C6—H6A	109.5	H51—N5—H52	112.4 (18)
C5—C6—H6B	109.5	C1—S1—C3	90.43 (5)
H6A—C6—H6B	109.5	HW1—OW1—HW2	106 (3)

N2—C2—C3—C5	175.76 (11)	C4—C2—N2—C1	177.27 (11)
C4—C2—C3—C5	−2.4 (2)	C3—C5—N3—N4	177.15 (9)
N2—C2—C3—S1	−0.57 (12)	C6—C5—N3—N4	−0.16 (18)
C4—C2—C3—S1	−178.69 (11)	N5—C7—N4—N3	−0.63 (16)
C2—C3—C5—N3	177.59 (11)	S2—C7—N4—N3	178.17 (8)
S1—C3—C5—N3	−6.25 (13)	C5—N3—N4—C7	−174.48 (10)
C2—C3—C5—C6	−4.92 (19)	N1—C1—S1—C3	177.38 (12)
S1—C3—C5—C6	171.25 (10)	N2—C1—S1—C3	−2.17 (9)
N1—C1—N2—C2	−177.21 (12)	C2—C3—S1—C1	1.55 (9)
S1—C1—N2—C2	2.34 (13)	C5—C3—S1—C1	−175.38 (9)
C3—C2—N2—C1	−1.15 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1···Cl1ⁱ	0.79 (3)	2.45 (3)	3.2298 (13)	171 (3)
N2—H2···Cl1ⁱⁱ	0.853 (18)	2.277 (18)	3.0812 (11)	157.2 (15)
OW1—HW2···Cl1	0.71 (3)	2.50 (3)	3.2111 (14)	178 (3)
N1—H11···Cl1ⁱⁱⁱ	0.78 (3)	2.81 (2)	3.2398 (15)	117.0 (18)
N1—H12···OW1^iv	0.87 (2)	1.97 (2)	2.8354 (19)	174 (2)
N4—H41···S2^v	0.943 (16)	2.686 (16)	3.6223 (11)	172.0 (14)
N5—H51···Cl1^vi	0.81 (2)	2.54 (2)	3.3243 (13)	164.9 (18)
N5—H52···OW1^vii	0.80 (2)	2.326 (19)	2.9899 (17)	141.2 (19)
N5—H52···N3	0.80 (2)	2.36 (2)	2.6306 (16)	100.6 (15)
C6—H6C···N4	0.96	2.48	2.8433 (18)	102
C6—H6C···S2^v	0.96	2.67	3.4923 (15)	143

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

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

Contact	Distance	Symmetry code
H52···OW1	2.33	x, 1 + y, z
C1···N5	3.37	1 + x, y, z
C7···H4A	2.83	-1 + x, 1 + y, z
H6C···S2	2.67	-x, 2 - y, -z
H4C···S2	3.08	1 - x, 2 - y, -z
H2···Cl1	2.28	1 + x, y, z
H11···Cl1	2.81	2 - x, 1 - y, 1 - z
H12···OW1	1.97	1 - x, 1 - y, 1 - z
N1···N1	3.27	2 - x, 1 - y, 1 - z
H51···Cl1	2.54	-1 + x, 1 + y, z
C6···C4	3.55	2 - x, 1 - y, -z
Cl1···HW2	2.50	x, y, z
Cl1···HW1	2.45	1 - x, -y, 1 - z

Acknowledgements

This study was supported by Baku State University, Erciyes University, Tribhuvan University and Universidad de Antofagasta. Authors' contributions are as follows. Conceptualization, EZH, KAA and AMM; methodology, EZH, IB and MA; investigation, EZH and IB; writing (original draft), MA and AB; writing (review and editing of the manuscript), MA and EZH; visualization, MA, FNN and IB; funding acquisition, EZH, AB and IB; resources, AB, IB and MA; supervision, MA and AMM

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