Crystal structure and Hirshfeld surface analysis of (E)-3-(benzyl­idene­amino)-5-phenyl­thia­zolidin-2-iminium bromide

Duruskari, G.S.; Akkurt, M.; Mammadova, G.Z.; Chyrka, T.; Maharramov, A.M.

doi:10.1107/S2056989020001899

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 76| Part 3| March 2020| Pages 427-431

https://doi.org/10.1107/S2056989020001899

Open

access

Crystal structure and Hirshfeld surface analysis of (E)-3-(benzylideneamino)-5-phenylthiazolidin-2-iminium bromide

Gulnara Sh. Duruskari,^a Mehmet Akkurt,^b Gunay Z. Mammadova,^a Taras Chyrka ^c ^* and Abel M. Maharramov ^a

^aOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az, 1148 Baku, Azerbaijan, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^cDepartment of Theoretical and Industrial Heat Engineering (TPT), National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", 03056, Kyiv, Ukraine
^*Correspondence e-mail: mustford@ukr.net

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 22 January 2020; accepted 10 February 2020; online 21 February 2020)

The central thiazolidine ring of the title salt, C₁₆H₁₆N₃S⁺·Br⁻, adopts an envelope conformation, with the C atom bearing the phenyl ring as the flap atom. In the crystal, the cations and anions are linked by N—H⋯Br hydrogen bonds, forming chains parallel to the b-axis direction. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (46.4%), C⋯H/H⋯C (18.6%) and H⋯Br/Br⋯H (17.5%) interactions.

Keywords: crystal structure; charge assisted hydrogen bonding; thiazolidine ring; envelope conformation; Hirshfeld surface analysis.

CCDC reference: 1837123

1. Chemical context

Sulfur and nitrogen-containing heterocycles maintain their importance as key fragments of drugs and medicinally active compounds (Pathania et al., 2019 ). Moreover, azomethine-containing structural motifs have been widely employed for industrial purposes as they exhibit a broad range of biological activities, and are used in synthesis, catalysis and the design of materials (Gurbanov et al., 2017 , 2018 ; Mahmoudi et al., 2018a ,b ,c ; Mamedov et al., 2018 ). Nowadays, N-ligands are key players in a wide diversity of fields, namely in coordination, metal–organic, pharmaceutical and medicinal chemistry, biologically active compounds, catalysis, non-covalent interactions and supramolecular assemblies (Maharramov et al., 2011 , 2018 ; Mahmudov et al., 2013 , 2014 , 2017a ,b , 2019 ; Mamedov et al., 2015 ). In our previous studies we have reported on the molecular structural properties of a series of 5-phenylthiazolidin-2-imine derivatives (Akkurt et al., 2018a ,b ; Duruskari et al., 2019a ,b ; Khalilov et al., 2019 ; Maharramov et al., 2019 ). Following further study in this field, herein we report the crystal structure and Hirshfeld surface analysis of the title compound, (E)-3-(benzylideneamino)-5-phenylthiazolidin-2-iminium bromide.

2. Structural commentary

The thiazolidine ring (S1/N2/C1–C3) in the cation of the title salt (Fig. 1) adopts an envelope conformation, with the C atom bearing the phenyl ring as the flap atom; the puckering parameters are Q(2) = 0.318 (3) Å and φ(2) = 42.0 (5)°. The mean plane of the thiazolidine ring makes dihedral angles of 18.28 (15) and 83.19 (15)°, respectively, with the C5–C10 and C11–C16 phenyl rings of the 3-(benzylideneamino) and 5-phenylthiazolidin groups, while the dihedral angle between them is 82.54 (15)°. The torsion angle of the N2—N1—C4—C5 bridge that links the thiazolidine and 3-(benzylideneamino) units is −175.7 (3)°.

Figure 1
The molecular structure of the title salt, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The interionic hydrogen bond is shown as a dashed line.

3. Supramolecular features

In the crystal, adjacent cations and anions are linked by pairs of N—H⋯Br hydrogen bonds (Table 1, Fig. 2), forming chains running parallel to the b-axis direction. C—H⋯π interactions or π–π stacking interactions contributing to the stabilization of the crystal packing are not observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Br1	0.90	2.37	3.258 (3)	168
N3—H3B⋯Br1ⁱ	0.90	2.55	3.399 (3)	158
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view of the crystal packing showing the formation of chains parallel to the b axis through N—H⋯Br hydrogen bonds (dashed lines).

4. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) of the title compound was generated by CrystalExplorer 3.1 (Wolff et al., 2012 ), and comprises d_norm surface plots and two-dimensional fingerprint plots (Spackman & McKinnon, 2002 ). A d_norm surface plot of the title compound mapped over d_norm using a standard surface resolution with a fixed colour scale of −0.3485 (red) to 1.3503 a.u. (blue) is shown in Fig. 3. The dark-red spots on the d_norm surface arise as a result of short interatomic contacts (Table 2), while the other weaker intermolecular interactions appear as light-red spots.

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

Contact	Distance	Symmetry operation
Br1⋯H3A (N3)	2.37	x, y, z
Br1⋯H3B (N3)	2.55	1 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
Br1⋯H14A (C14)	3.14	−x, 1 − y, 1 − z
Br1⋯H4A (C4)	2.96	x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
Br1⋯H12A (C12)	3.02	x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z

Figure 3
View of the three-dimensional Hirshfeld surface of the title salt plotted over d_norm.

The shape index of the Hirshfeld surface is a tool to visualize π–·π stacking interactions by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 4 clearly suggests that there are no π–π interactions present in the title compound. Fig. 5(a) shows the two-dimensional fingerprint of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode (Tables 1 and 2). The fingerprint plots delineated into H⋯H (46.4%), C⋯H/H⋯C (18.6%), H⋯Br/Br⋯H (17.5%), H⋯S/S⋯H (4.5%) and C⋯N/N⋯C (3.7%) contacts are shown in Fig. 5b–f.

Figure 4
Hirshfeld surface of the title salt plotted over shape-index.

Figure 5
The Hirshfeld surface representations and the full two-dimensional fingerprint plots for the title salt, showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) H⋯Br/Br⋯H, (e) H⋯S/S⋯H and (f) C⋯N/N⋯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.

The most significant intermolecular interactions are the H⋯H interactions (46.4%) (Fig. 5b). All of the contributions to the Hirshfeld surface are given in Table 3. The large number of H⋯H, C⋯H/H⋯C and H⋯Br/Br⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

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

Contact	Percentage contribution
H⋯H	46.4
C⋯H/H⋯C	18.6
H⋯Br/Br⋯H	17.5
H⋯S/S⋯H	4.5
C⋯N/N⋯C	3.7
C⋯S/S⋯C	3.0
H⋯N/N⋯H	2.6
C⋯C	2.3
C⋯Br/Br⋯C	0.9
N⋯S/S⋯N	0.5
N⋯N	0.2

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, February 2019; Groom et al., 2016 ) for 2-thiazolidiniminium compounds gave ten hits, viz. MOJGUQ (Duruskari et al., 2019a), XOWXAL (Duruskari et al., 2019b), BOBWIB (Khalilov et al., 2019), UDELUN (Akkurt et al., 2018a), WILBIC (Marthi et al., 1994 ), WILBOI (Marthi et al., 1994), WILBOI01 (Marthi et al., 1994), YITCEJ (Martem'yanova et al., 1993a ), YITCAF (Martem'yanova et al., 1993b ) and YOPLUK (Marthi et al., 1995 ).

In the crystal of MOJGUQ (Duruskari et al., 2019a), centrosymmetrically related cations and anions are linked into dimeric units via N—-H⋯Br hydrogen bonds, which are further connected by weak C—H⋯Br contacts into chains parallel to the a axis. Furthermore, C—H⋯π interactions and π–π stacking interactions [centroid-to-centroid distance = 3.897 (2) Å] between the major components of the disordered phenyl ring contribute to the stabilization of the molecular packing. In the crystal of XOWXAL (Duruskari et al., 2019b), the thiazolidine ring adopts an envelope conformation. N—H⋯Br hydrogen bonds link the components into a three-dimensional network. Weak π–π stacking interactions between the phenyl rings of adjacent cations also contribute to the molecular packing. In the crystal of BOBWIB (Khalilov et al., 2019), the central thiazolidine ring adopts an envelope conformation. In the crystal, centrosymmetrically related cations and anions are linked into dimeric units via N—H⋯Br hydrogen bonds, which are further connected by weak C—H⋯Br hydrogen bonds into chains parallel to [110]. In the crystal of UDELUN (Akkurt et al., 2018a), C—H⋯Br and N—H⋯Br hydrogen bonds link the components into a three-dimensional network with the cations and anions stacked along the b-axis direction. Weak C—H⋯π interactions, which only involve the minor disorder component of the ring, also contribute to the molecular packing. In addition, there are also inversion-related Cl⋯Cl halogen bonds and C-–Cl⋯π(ring) contacts. In the other structures, the 3-N atom carries a C–substituent instead of an N–substituent as found in the title compound. Three of them were determined to be racemic (WILBIC; Marthi et al., 1994) and two optically active samples (WILBOI and WILBOI01; Marthi et al., 1994) of 3-(2′-chloro-2′-phenylethyl)-2-thiazolidiniminium p-toluenesulfonate. In all three structures, the most disordered fragment is the asymmetric C atom and the Cl atom attached to it. The disorder of the cation in the racemate corresponds to the presence of both enantiomers at each site in the ratio 0.821 (3):0.179 (3). The system of hydrogen bonds connecting two cations and two anions into 12-membered rings is identical in the racemic and in the optically active crystals. YITCEJ (Martem'yanova et al., 1993a), is a product of the interaction of 2-amino-5-methylthiazoline with methyl iodide, with alkylation at the endocylic nitrogen atom, while YITCAF (Martem'yanova et al., 1993b) is a product of the reaction of 3-nitro-5-methoxy-, 3-nitro-5-chloro-, and 3-bromo-5-nitrosalicylaldehyde with the heterocyclic base to form the salt-like complexes.

6. Synthesis and crystallization

To the solution of 3-amino-5-phenylthiazolidin-2-iminium bromide (1 mmol) in 20 mL of ethanol was added benzaldehyde (1 mmol) and the mixture was refluxed for 2 h. After cooling down to room temperature, the reaction product precipitated as colourless single crystals, which were collected by filtration and washed with cold acetone (yield 76%), m.p. 519 K. Analysis calculated for C₁₆H₁₆BrN₃S (M_r = 362.29): C, 53.04; H, 4.45; N, 11.60. Found: C, 53.01; H, 4.42; N, 11.56%. ¹H NMR (300 MHz, DMSO-d₆) : 4.58 (k, 1H, CH₂, ³J_H–H = 6.9); 4,89 (t, 1H, CH₂, ³J_H–H =8.1); 5.60 (t, 1H, CH-Ar, ³J_H–H =7.5); 7.37–8.07 (m, 10H, 10Ar-H); 8.44 (s, 1H, CH=), 10.35 (s, 2H, NH=). ¹³C NMR (75 MHz, DMSO-d₆): 45.36, 55.91, 127.76, 128.65, 128.82, 128.86, 129.09, 131.54, 132.85, 137.48, 151.11, 167.84. MS (ESI), m/z: 282.30 [C₁₆H₁₆N₃S]⁺ and 79.88 Br⁻.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All H atoms were placed at calculated positions (N—H = 0.90 Å and C—H = 0.93–0.98 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(N, C). The distances between the carbon atoms of two phenyl groups were constrained with a DFIX instruction [DFIX 1.40 0.02 C C].

Table 4
Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₃S⁺·Br⁻
M_r	362.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.138 (8), 8.336 (5), 15.872 (9)
β (°)	93.910 (16)
V (Å³)	1602.3 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.69
Crystal size (mm)	0.21 × 0.18 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.582, 0.713
No. of measured, independent and observed [I > 2σ(I)] reflections	23979, 3314, 2742
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 1.06
No. of reflections	3314
No. of parameters	190
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.60
Computer programs: APEX2 and SAINT (Bruker, 2003), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1837123

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001899/rz5269sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001899/rz5269Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(E)-3-(Benzylideneamino)-5-phenylthiazolidin-2-iminium bromide top

Crystal data top

C₁₆H₁₆N₃S⁺·Br⁻	F(000) = 736
M_r = 362.29	D_x = 1.502 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.138 (8) Å	Cell parameters from 9891 reflections
b = 8.336 (5) Å	θ = 2.8–26.4°
c = 15.872 (9) Å	µ = 2.69 mm⁻¹
β = 93.910 (16)°	T = 296 K
V = 1602.3 (17) Å³	Plate, colourless
Z = 4	0.21 × 0.18 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	2742 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.049
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.5°, θ_min = 2.6°
T_min = 0.582, T_max = 0.713	h = −15→15
23979 measured reflections	k = −10→10
3314 independent reflections	l = −19→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0521P)² + 1.4845P] where P = (F_o² + 2F_c²)/3
3314 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.74 e Å⁻³
12 restraints	Δρ_min = −0.60 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
Br1	0.36371 (3)	0.40930 (5)	0.77766 (2)	0.05996 (15)
S1	0.27771 (6)	0.50993 (10)	0.55109 (5)	0.0478 (2)
N1	0.52247 (19)	0.7685 (3)	0.49030 (15)	0.0411 (5)
N2	0.42403 (19)	0.6853 (3)	0.48814 (15)	0.0438 (5)
N3	0.4551 (2)	0.6390 (3)	0.63168 (16)	0.0500 (6)
H3A	0.431514	0.589059	0.677388	0.060*
H3B	0.509254	0.711959	0.640888	0.060*
C1	0.3432 (2)	0.6653 (4)	0.41558 (19)	0.0467 (7)
H1A	0.380449	0.651339	0.363896	0.056*
H1B	0.295261	0.758163	0.409430	0.056*
C2	0.2763 (3)	0.5140 (4)	0.4348 (2)	0.0489 (7)
H2A	0.315568	0.419380	0.415778	0.059*
C3	0.3971 (2)	0.6205 (3)	0.56063 (18)	0.0412 (6)
C4	0.5460 (2)	0.8450 (4)	0.42487 (19)	0.0440 (6)
H4A	0.495374	0.850348	0.378264	0.053*
C5	0.6520 (2)	0.9241 (3)	0.42299 (14)	0.0416 (6)
C6	0.7284 (2)	0.9221 (4)	0.49283 (19)	0.0513 (7)
H6A	0.710541	0.874346	0.543049	0.062*
C7	0.8319 (2)	0.9924 (4)	0.4867 (2)	0.0663 (10)
H7A	0.883751	0.988871	0.532539	0.080*
C8	0.8581 (3)	1.0679 (4)	0.41226 (19)	0.0652 (10)
H8A	0.927072	1.114885	0.408687	0.078*
C9	0.7808 (2)	1.0730 (4)	0.3432 (2)	0.0651 (10)
H9A	0.797532	1.124866	0.293831	0.078*
C10	0.6782 (2)	0.9998 (4)	0.34862 (17)	0.0551 (8)
H10A	0.626928	1.001586	0.302329	0.066*
C11	0.1609 (2)	0.5115 (3)	0.39571 (17)	0.0446 (6)
C12	0.1299 (2)	0.3891 (4)	0.3387 (2)	0.0613 (9)
H12A	0.180793	0.310914	0.325946	0.074*
C13	0.0225 (2)	0.3838 (5)	0.3009 (2)	0.0690 (10)
H13A	0.002162	0.302592	0.262799	0.083*
C14	−0.0538 (3)	0.5001 (4)	0.3205 (2)	0.0661 (10)
H14A	−0.124515	0.498545	0.293897	0.079*
C15	−0.0251 (3)	0.6186 (4)	0.3794 (2)	0.0683 (10)
H15A	−0.076995	0.693888	0.394077	0.082*
C16	0.0820 (2)	0.6235 (4)	0.4163 (2)	0.0631 (9)
H16A	0.101386	0.703134	0.455623	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0594 (2)	0.0700 (3)	0.0489 (2)	−0.01088 (16)	−0.00776 (15)	0.01409 (15)
S1	0.0461 (4)	0.0511 (4)	0.0467 (4)	−0.0073 (3)	0.0065 (3)	0.0068 (3)
N1	0.0379 (12)	0.0421 (13)	0.0432 (13)	−0.0028 (10)	0.0028 (10)	0.0008 (10)
N2	0.0387 (12)	0.0496 (14)	0.0429 (13)	−0.0054 (10)	0.0013 (10)	0.0085 (11)
N3	0.0544 (15)	0.0552 (15)	0.0405 (13)	−0.0076 (12)	0.0042 (11)	0.0037 (11)
C1	0.0426 (15)	0.0550 (17)	0.0418 (15)	−0.0053 (13)	−0.0020 (12)	0.0096 (13)
C2	0.0471 (16)	0.0482 (17)	0.0515 (17)	−0.0002 (13)	0.0038 (13)	−0.0012 (14)
C3	0.0406 (14)	0.0414 (14)	0.0419 (15)	0.0029 (11)	0.0062 (12)	0.0012 (12)
C4	0.0436 (15)	0.0431 (15)	0.0449 (15)	−0.0018 (12)	0.0005 (12)	0.0055 (12)
C5	0.0422 (15)	0.0334 (14)	0.0497 (16)	−0.0004 (11)	0.0063 (12)	−0.0022 (12)
C6	0.0536 (18)	0.0424 (16)	0.0566 (18)	−0.0077 (13)	−0.0055 (15)	0.0040 (14)
C7	0.053 (2)	0.055 (2)	0.087 (3)	−0.0103 (16)	−0.0162 (18)	−0.0012 (19)
C8	0.0486 (19)	0.059 (2)	0.089 (3)	−0.0127 (16)	0.0169 (19)	−0.0111 (19)
C9	0.070 (2)	0.068 (2)	0.059 (2)	−0.0205 (19)	0.0244 (18)	−0.0054 (17)
C10	0.059 (2)	0.060 (2)	0.0468 (17)	−0.0132 (16)	0.0068 (15)	−0.0005 (15)
C11	0.0407 (15)	0.0474 (16)	0.0457 (15)	−0.0051 (12)	0.0039 (12)	0.0059 (13)
C12	0.061 (2)	0.059 (2)	0.065 (2)	0.0023 (16)	0.0165 (17)	−0.0059 (17)
C13	0.063 (2)	0.082 (3)	0.061 (2)	−0.022 (2)	0.0058 (18)	−0.0193 (19)
C14	0.054 (2)	0.083 (3)	0.061 (2)	−0.0111 (19)	0.0019 (17)	0.010 (2)
C15	0.055 (2)	0.062 (2)	0.088 (3)	0.0063 (17)	0.0043 (19)	0.007 (2)
C16	0.060 (2)	0.0477 (18)	0.083 (3)	−0.0009 (15)	0.0096 (18)	−0.0116 (17)

Geometric parameters (Å, º) top

S1—C3	1.716 (3)	C6—H6A	0.9300
S1—C2	1.844 (3)	C7—C8	1.394 (2)
N1—C4	1.268 (4)	C7—H7A	0.9300
N1—N2	1.380 (3)	C8—C9	1.394 (2)
N2—C3	1.332 (4)	C8—H8A	0.9300
N2—C1	1.470 (4)	C9—C10	1.394 (2)
N3—C3	1.297 (4)	C9—H9A	0.9300
N3—H3A	0.9000	C10—H10A	0.9300
N3—H3B	0.9001	C11—C16	1.392 (2)
C1—C2	1.542 (4)	C11—C12	1.398 (2)
C1—H1A	0.9700	C12—C13	1.397 (2)
C1—H1B	0.9700	C12—H12A	0.9300
C2—C11	1.493 (4)	C13—C14	1.391 (2)
C2—H2A	0.9800	C13—H13A	0.9300
C4—C5	1.447 (4)	C14—C15	1.389 (2)
C4—H4A	0.9300	C14—H14A	0.9300
C5—C10	1.3944 (19)	C15—C16	1.390 (2)
C5—C6	1.396 (2)	C15—H15A	0.9300
C6—C7	1.395 (2)	C16—H16A	0.9300

C3—S1—C2	91.65 (14)	C5—C6—H6A	120.3
C4—N1—N2	118.4 (2)	C8—C7—C6	120.5 (3)
C3—N2—N1	116.4 (2)	C8—C7—H7A	119.8
C3—N2—C1	116.2 (2)	C6—C7—H7A	119.8
N1—N2—C1	127.4 (2)	C9—C8—C7	120.0 (3)
C3—N3—H3A	117.5	C9—C8—H8A	120.0
C3—N3—H3B	124.6	C7—C8—H8A	120.0
H3A—N3—H3B	116.8	C8—C9—C10	119.6 (3)
N2—C1—C2	105.7 (2)	C8—C9—H9A	120.2
N2—C1—H1A	110.6	C10—C9—H9A	120.2
C2—C1—H1A	110.6	C9—C10—C5	120.4 (3)
N2—C1—H1B	110.6	C9—C10—H10A	119.8
C2—C1—H1B	110.6	C5—C10—H10A	119.8
H1A—C1—H1B	108.7	C16—C11—C12	118.8 (3)
C11—C2—C1	114.9 (3)	C16—C11—C2	122.2 (2)
C11—C2—S1	111.1 (2)	C12—C11—C2	118.9 (2)
C1—C2—S1	104.1 (2)	C13—C12—C11	120.2 (3)
C11—C2—H2A	108.8	C13—C12—H12A	119.9
C1—C2—H2A	108.8	C11—C12—H12A	119.9
S1—C2—H2A	108.8	C14—C13—C12	119.9 (3)
N3—C3—N2	123.5 (3)	C14—C13—H13A	120.1
N3—C3—S1	123.1 (2)	C12—C13—H13A	120.1
N2—C3—S1	113.4 (2)	C15—C14—C13	120.4 (3)
N1—C4—C5	119.7 (3)	C15—C14—H14A	119.8
N1—C4—H4A	120.1	C13—C14—H14A	119.8
C5—C4—H4A	120.1	C14—C15—C16	119.3 (3)
C10—C5—C6	120.0 (3)	C14—C15—H15A	120.3
C10—C5—C4	118.6 (2)	C16—C15—H15A	120.3
C6—C5—C4	121.4 (2)	C15—C16—C11	121.3 (3)
C7—C6—C5	119.5 (3)	C15—C16—H16A	119.3
C7—C6—H6A	120.3	C11—C16—H16A	119.3

C4—N1—N2—C3	−173.3 (3)	C5—C6—C7—C8	1.7 (5)
C4—N1—N2—C1	4.2 (4)	C6—C7—C8—C9	−0.3 (6)
C3—N2—C1—C2	−24.6 (4)	C7—C8—C9—C10	−1.1 (6)
N1—N2—C1—C2	157.9 (3)	C8—C9—C10—C5	1.0 (6)
N2—C1—C2—C11	151.9 (3)	C6—C5—C10—C9	0.4 (5)
N2—C1—C2—S1	30.1 (3)	C4—C5—C10—C9	−177.9 (3)
C3—S1—C2—C11	−148.7 (2)	C1—C2—C11—C16	−63.2 (4)
C3—S1—C2—C1	−24.5 (2)	S1—C2—C11—C16	54.7 (4)
N1—N2—C3—N3	3.6 (4)	C1—C2—C11—C12	119.2 (3)
C1—N2—C3—N3	−174.1 (3)	S1—C2—C11—C12	−122.9 (3)
N1—N2—C3—S1	−176.5 (2)	C16—C11—C12—C13	2.5 (5)
C1—N2—C3—S1	5.8 (3)	C2—C11—C12—C13	−179.9 (3)
C2—S1—C3—N3	−168.0 (3)	C11—C12—C13—C14	−0.4 (6)
C2—S1—C3—N2	12.1 (2)	C12—C13—C14—C15	−2.1 (6)
N2—N1—C4—C5	−175.7 (3)	C13—C14—C15—C16	2.5 (6)
N1—C4—C5—C10	176.5 (3)	C14—C15—C16—C11	−0.3 (6)
N1—C4—C5—C6	−1.9 (5)	C12—C11—C16—C15	−2.1 (6)
C10—C5—C6—C7	−1.8 (5)	C2—C11—C16—C15	−179.7 (3)
C4—C5—C6—C7	176.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Br1	0.90	2.37	3.258 (3)	168
N3—H3B···Br1ⁱ	0.90	2.55	3.399 (3)	158

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

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

Contact	Distance	Symmetry operation
Br1···H3A (N3)	2.37	x, y, z
Br1···H3B (N3)	2.55	1 - x, - 1/2 + y, 3/2 - z
Br1···H14A (C14)	3.14	- x, 1 - y, 1 - z
Br1···H4A (C4)	2.96	x, 3/2 - y, 1/2 + z
Br1···H12A (C12)	3.02	x, 1/2 - y, 1/2 + z

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

Contact	Percentage contribution
H···H	46.4
C···H/H···C	18.6
H···Br/Br···H	17.5
H···S/S···H	4.5
C···N/N···C	3.7
C···S/S···C	3.0
H···N/N···H	2.6
C···C	2.3
C···Br/Br···C	0.9
N···S/S···N	0.5
N···N	0.2

References

Akkurt, M., Duruskari, G. S., Toze, F. A. A., Khalilov, A. N. & Huseynova, A. T. (2018a). Acta Cryst. E74, 1168–1172. CSD CrossRef IUCr Journals Google Scholar
Akkurt, M., Maharramov, A. M., Duruskari, G. S., Toze, F. A. A. & Khalilov, A. N. (2018b). Acta Cryst. E74, 1290–1294. CSD CrossRef IUCr Journals Google Scholar
Bruker (2003). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Duruskari, G. S., Khalilov, A. N., Akkurt, M., Mammadova, G. Z., Chyrka, T. & Maharramov, A. M. (2019a). Acta Cryst. E75, 1544–1547. CSD CrossRef IUCr Journals Google Scholar
Duruskari, G. S., Khalilov, A. N., Akkurt, M., Mammadova, G. Z., Chyrka, T. & Maharramov, A. M. (2019b). Acta Cryst. E75, 1175–1179. CSD CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gurbanov, A. V., Maharramov, A. M., Zubkov, F. I., Saifutdinov, A. M. & Guseinov, F. I. (2018). Aust. J. Chem. 71, 190–194. Web of Science CrossRef CAS Google Scholar
Gurbanov, A. V., Mahmudov, K. T., Kopylovich, M. N., Guedes da Silva, F. M., Sutradhar, M., Guseinov, F. I., Zubkov, F. I., Maharramov, A. M. & Pombeiro, A. J. L. (2017). Dyes Pigments, 138, 107–111. Web of Science CSD CrossRef CAS Google Scholar
Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). IUCrJ, 2, 563–574. Web of Science CSD CrossRef CAS PubMed IUCr Journals Google Scholar
Khalilov, A. N., Atioğlu, Z., Akkurt, M., Duruskari, G. S., Toze, F. A. A. & Huseynova, A. T. (2019). Acta Cryst. E75, 662–666. Web of Science CSD CrossRef IUCr Journals Google Scholar
Maharramov, A. M., Duruskari, G. Sh., Mammadova, G. Z., Khalilov, A. N., Aslanova, J. M., Cisterna, J., Cárdenas, A. & Brito, I. (2019). J. Chil. Chem. Soc. 64, 4441–4447. CSD CrossRef CAS Google Scholar
Maharramov, A. M., Khalilov, A. N., Gurbanov, A. V., Allahverdiyev, M. A. & Ng, S. W. (2011). Acta Cryst. E67, o721. Web of Science CSD CrossRef IUCr Journals Google Scholar
Maharramov, A. M., Shikhaliyev, N. Q., Suleymanova, G. T., Gurbanov, A. V., Babayeva, G. V., Mammadova, G. Z., Zubkov, F. I., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Dyes Pigments, 159, 135–141. Web of Science CrossRef CAS Google Scholar
Mahmoudi, G., Seth, S. K., Bauzá, A., Zubkov, F. I., Gurbanov, A. V., White, J., Stilinović, V., Doert, Th. & Frontera, A. (2018c). CrystEngComm, 20, 2812–2821. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Zangrando, E., Mitoraj, M. P., Gurbanov, A. V., Zubkov, F. I., Moosavifar, M., Konyaeva, I. A., Kirillov, A. M. & Safin, D. A. (2018a). New J. Chem. 42, 4959–4971. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Zaręba, J. K., Gurbanov, A. V., Bauzá, A., Zubkov, F. I., Kubicki, M., Stilinović, V., Kinzhybalo, V. & Frontera, A. (2018b). Eur. J. Inorg. Chem. pp. 4763–4772. Google Scholar
Mahmudov, K. T., Gurbanov, A. V., Guseinov, F. I. & Guedes da Silva, M. F. C. (2019). Coord. Chem. Rev. 387, 32–46. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2017a). Dalton Trans. 46, 10121–10138. Web of Science CrossRef CAS PubMed Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2017b). Coord. Chem. Rev. 345, 54–72. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Maharramov, A. M., Kurbanova, M. M., Gurbanov, A. V. & Pombeiro, A. J. L. (2014). Coord. Chem. Rev. 265, 1–37. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Kopylovich, M. N. & Pombeiro, A. J. L. (2013). Coord. Chem. Rev. 257, 1244–1281. Web of Science CrossRef CAS Google Scholar
Mamedov, I. G., Bayramov, M. R., Salamova, A. E. & Maharramov, A. M. (2015). Indian J. Chem. 54B, 1518–1527. CAS Google Scholar
Mamedov, I. G., Farzaliyeva, A. E., Mamedova, Y. V., Hasanova, N. N., Bayramov, M. R. & Maharramov, A. M. (2018). Indian J. Chem. 57B, 1310–1314. CAS Google Scholar
Martem'yanova, N. A., Chunaev, Y. M., Przhiyalgovskaya, N. M., Kurkovskaya, L. N., Filipenko, O. S. & Aldoshin, S. M. (1993a). Khim. Geterotsikl. Soedin. pp. 415–419. Google Scholar
Martem'yanova, N. A., Chunaev, Y. M., Przhiyalgovskaya, N. M., Kurkovskaya, L. N., Filipenko, O. S. & Aldoshin, S. M. (1993b). Khim. Geterotsikl. Soedin. pp. 420–425. Google Scholar
Marthi, K., Larsen, M., Ács, M., Bálint, J. & Fogassy, E. (1995). Acta Chem. Scand. 49, 20–27. CSD CrossRef CAS Web of Science Google Scholar
Marthi, K., Larsen, S., Ács, M., Bálint, J. & Fogassy, E. (1994). Acta Cryst. B50, 762–771. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Pathania, S., Narang, R. K. & Rawal, R. K. (2019). Eur. J. Med. Chem. 180, 486–508. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & McKinnon, J. J. (2002). CrystEngComm, 4, 378–392. Web of Science CrossRef CAS Google Scholar
Spackman, M. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. University of Western Australia. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.