Crystal structure and Hirshfeld surface analysis of (E)-3-[(4-fluoro­benzyl­idene)amino]-5-phenyl­thia­zolidin-2-iminium bromide

Khalilov, A.N.; Atioğlu, Z.; Akkurt, M.; Duruskari, G.S.; Toze, F.A.A.; Huseynova, A.T.

doi:10.1107/S2056989019004973

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 662-666

https://doi.org/10.1107/S2056989019004973

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Crystal structure and Hirshfeld surface analysis of (E)-3-[(4-fluorobenzylidene)amino]-5-phenylthiazolidin-2-iminium bromide

Ali N. Khalilov,^a,^b Zeliha Atioğlu,^c Mehmet Akkurt,^d Gulnara Sh. Duruskari,^a Flavien A. A. Toze ^e ^* and Afet T. Huseynova ^a

^aOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az 1148, Baku, Azerbaijan, ^bDepartment of Physics and Chemistry, "Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), H. Aliyev str. 135, Az 1063, Baku, Azerbaijan, ^cİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^eDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of Cameroon
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 2 April 2019; accepted 11 April 2019; online 18 April 2019)

In the cation of the title salt, C₁₆H₁₅FN₃S⁺·Br⁻, the phenyl ring is disordered over two sets of sites with a refined occupancy ratio of 0.503 (4):0.497 (4). The mean plane of the thiazolidine ring makes dihedral angles of 13.51 (14), 48.6 (3) and 76.5 (3)° with the fluorophenyl ring and the major- and minor-disorder components of the phenyl ring, respectively. 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]. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (44.3%), Br⋯H/H⋯Br (16.8%), C⋯H/H⋯C (13.9%), F⋯H/H⋯F (10.3%) and S⋯H/H⋯S (3.8%) interactions.

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

CCDC reference: 1909594

1. Chemical context

Noncovalent interactions, both intermolecular and intramolecular, occur in virtually every substance and play an important role in the synthesis, catalysis, design of materials and biological processes (Akbari et al., 2017 ; Gurbanov et al., 2018 ; Kopylovich et al., 2011 ; Maharramov et al., 2010 ; Mahmoudi et al., 2018a ,b ,c ; Mahmudov et al., 2011 , 2013 , 2014a ,b , 2015 , 2017a ,b , 2019 ; Shixaliyev et al., 2013 , 2018 ). On the other hand, Schiff bases and related hydrazone ligands and their complexes have attracted attention over the past decades due to their potential biological, pharmacological and analytical applications (Kopylovich et al., 2011; Mahmoudi et al., 2018a,b,c; Mahmudov et al., 2013). Hetercyclic amines are also widely used in the synthesis of Schiff bases, which provide different kinds of noncovalent interactions. As a further study in this field, we report herein the crystal structure and Hirshfeld surface analysis of the title compound.

2. Structural commentary

The thiazolidine ring (S1/N2/C1–C3) in the cation of the title salt (Fig. 1) adopts an envelope conformation, with puckering parameters of Q(2) = 0.321 (3) Å and φ(2) = 43.3 (5)°. The mean plane of the thiazolidine ring makes dihedral angles of 13.51 (14), 48.6 (3) and 76.5 (3)° with the fluorophenyl ring (C5–C10) and the major- and minor-disorder components (C11–C16 and C11′–C16′) of the phenyl ring, respectively. The N2—N1—C4—C5 bridge that links the thiazolidine and 4-fluorophenyl rings has a torsion angle of −177.36 (19)°.

Figure 1
The molecular structure of the title salt. Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as spheres of arbitrary radius. The minor-disorder component has been omitted for clarity

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, centrosymmetrically related cations and anions are linked via pairs of N—H⋯Br hydrogen bonds (Table 1) into dimeric units forming rings of R₄²(8) graph-set motif (Fig. 2). The dimers are further connected by weak C—H⋯Br interactions to form chains running parallel to [110].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Br1	0.90	2.36	3.2557 (18)	172
N3—H3B⋯Br1ⁱ	0.90	2.55	3.3552 (18)	150
C4—H4A⋯Br1ⁱⁱ	0.93	2.99	3.726 (2)	137
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y+1, z.

Figure 2
A view of the intermolecular N—H⋯Br hydrogen bonds of the title salt in the unit cell. The minor-disorder component has been omitted for clarity

Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and intermolecular interactions in the crystal structure. The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) of the title salt was generated by CrystalExplorer3.1 (Wolff et al., 2012 ), and comprised d_norm surface plots and 2D fingerprint plots (Spackman & McKinnon, 2002 ). The plots of the Hirshfeld surface mapped over d_norm using a standard surface resolution with a fixed colour scale of −1.4747 (red) to 1.2166 a.u. (blue) is shown in Fig. 3. This plot was generated to quantify and visualize the intermolecular interactions and to explain the observed crystal packing.

Figure 3
Hirshfeld surface of the title salt mapped with 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 suggest that there are no π–π interactions present in the title salt.

Figure 4
Hirshfeld surface of the title salt mapped with shape index.

Fig. 5(a) shows the 2D fingerprint of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode. These represent both the overall 2D fingerprint plots and those that represent H⋯H (44.3%), Br⋯H/H⋯Br (16.8%), C⋯H/H⋯C (13.9%), F⋯H/H⋯F (10.3%) and S⋯H/H⋯S (3.8%) contacts, respectively (Figs. 5b–f). The most significant intermolecular interactions are the H⋯H interactions (44.3%) (Fig. 6b). All the contributions to the Hirshfeld surface are given in Table 2.

Table 2
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title salt

Contact	Percentage contribution
H⋯H	44.3
Br⋯H/H⋯Br	16.8
C⋯H/H⋯C	13.9
F⋯H/H⋯F	10.3
S⋯H/H⋯S	3.8
N⋯C/C⋯N	3.6
S⋯C/C⋯S	2.7
N⋯H/H⋯N	1.8
C⋯C	1.5
N⋯N	0.7
Br⋯C/C⋯Br	0.3
S⋯N/N⋯S	0.3
F⋯C/C⋯F	0.2

Figure 5
The 2D fingerprint plots of the title salt, showing (a) all interactions, and delineated into (b) H⋯H, (c) Br⋯H/H⋯Br, (d) C⋯H/H⋯C, (e) F⋯H/H⋯F and (f) S⋯H/H⋯S 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].

3.1. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, update of November 2018; Groom et al., 2016 ) for 2-thiazolidiniminium compounds gave seven hits, viz. UDELUN (Akkurt et al., 2018 ), 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 UDELUN (Akkurt et al., 2018), 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 remaining structures, the 3-N atom carries a C-substituent instead of an N-substituent, as found in the title compound. The first three crystal structures were determined for 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 of these molecules 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 N 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.

4. Synthesis and crystallization

To a solution of 3-amino-5-phenylthiazolidin-2-iminium bromide (1 mmol) in ethanol (20 ml) was added 4-fluorobenzaldehyde (1 mmol). The mixture was refluxed for 2 h and then cooled. The reaction product precipitated from the reaction mixture as colourless single crystals, was collected by filtration and washed with cold acetone (yield 64%; m.p. 544–545 K). Analysis calculated (%) for C₁₆H₁₅BrFN₃S: C 50.53, H 3.98, N 11.05; found: C 50.47, H 3.93, N 11.00. ¹H NMR (300 MHz, DMSO-d₆) : 4.56 (k, 1H, CH₂, ³J_H-H = 6.6 Hz), 4,87 (t, 1H, CH₂, ³J_H-H = 7.8 Hz), 5.60 (t, 1H, CH-Ar, 3J_H-H = 7.8 Hz), 7.32–8.16 (m, 9H, 9Ar-H), 8.45 (s, 1H, CH=), 10.37 (s, 2H, NH₂). ¹³C NMR (75 MHz, DMSO-d₆): 45.39, 55.97, 116.05, 127.81, 128.91, 129.13, 129.60, 131.05, 131.17, 137.55, 150.00, 167.89. MS (ESI), m/z: 300.36 [C₁₆H₁₅FN₃S]⁺ and 79.88 Br⁻.

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined using a riding model, with N—H = 0.90 Å and C—H = 0.93–0.98 Å, and with U_iso(H) = 1.2U_eq(C,N). The phenyl ring in the cation is disordered over two sets of sites with an occupancy ratio of 0.503 (4):0.497 (4). Seven outliers (001; $[\overline{3}]$ 05; $[\overline{1}]$ 43; 010; $[\overline{2}]$ 75; $[\overline{2}]$ , $[\overline{1}]$ ,12; and 7 $[\overline{5}]$ 3) were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₁₅FN₃S⁺·Br⁻
M_r	380.28
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.0599 (3), 8.6086 (4), 12.7608 (5)
α, β, γ (°)	96.548 (2), 92.518 (2), 111.065 (2)
V (Å³)	817.39 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.65
Crystal size (mm)	0.16 × 0.12 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.664, 0.782
No. of measured, independent and observed [I > 2σ(I)] reflections	12009, 3321, 2672
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.04
No. of reflections	3321
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.48
Computer programs: APEX2 (Bruker, 2007 ), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2003 ).

Supporting information

CCDC reference: 1909594

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004973/rz5254sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004973/rz5254Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2003).

(E)-3-[(4-Fluorobenzylidene)amino]-5-phenylthiazolidin-2-iminium bromide top

Crystal data top

C₁₆H₁₅FN₃S⁺·Br⁻	Z = 2
M_r = 380.28	F(000) = 384
Triclinic, P1	D_x = 1.545 Mg m⁻³
a = 8.0599 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6086 (4) Å	Cell parameters from 5655 reflections
c = 12.7608 (5) Å	θ = 2.6–26.3°
α = 96.548 (2)°	µ = 2.65 mm⁻¹
β = 92.518 (2)°	T = 296 K
γ = 111.065 (2)°	Plate, colorless
V = 817.39 (6) Å³	0.16 × 0.12 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	2672 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.5°, θ_min = 2.7°
T_min = 0.664, T_max = 0.782	h = −10→7
12009 measured reflections	k = −10→10
3321 independent reflections	l = −14→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0376P)² + 0.2228P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3321 reflections	Δρ_max = 0.37 e Å⁻³
254 parameters	Δρ_min = −0.48 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	Occ. (<1)
Br1	0.28837 (4)	−0.06846 (3)	0.65093 (2)	0.07274 (12)
S1	0.50535 (9)	0.40641 (8)	0.72511 (4)	0.06317 (17)
F1	1.1652 (2)	0.6889 (3)	0.07197 (13)	0.0994 (6)
N1	0.7677 (2)	0.5288 (2)	0.48291 (13)	0.0510 (4)
C1	0.7491 (4)	0.6768 (3)	0.66453 (19)	0.0676 (7)
H1A	0.765957	0.780305	0.635640	0.081*
H1B	0.859205	0.688530	0.704392	0.081*
N2	0.6981 (3)	0.5342 (2)	0.57951 (13)	0.0540 (4)
C2	0.5974 (5)	0.6381 (4)	0.73431 (19)	0.0803 (9)
H2A	0.506784	0.680819	0.710523	0.096*
N3	0.5389 (3)	0.2468 (2)	0.54077 (14)	0.0564 (5)
H3A	0.472588	0.153018	0.566419	0.068*
H3B	0.598218	0.240158	0.483319	0.068*
C3	0.5851 (3)	0.3881 (3)	0.60334 (16)	0.0489 (5)
C4	0.8962 (3)	0.6588 (3)	0.46468 (18)	0.0583 (6)
H4A	0.943400	0.751707	0.516854	0.070*
C5	0.9692 (3)	0.6619 (3)	0.36204 (18)	0.0532 (5)
C6	1.0980 (3)	0.8092 (3)	0.3405 (2)	0.0691 (7)
H6A	1.139096	0.902914	0.392330	0.083*
C7	1.1660 (4)	0.8188 (4)	0.2431 (2)	0.0767 (8)
H7A	1.254083	0.916970	0.229104	0.092*
C8	1.1011 (3)	0.6810 (4)	0.1683 (2)	0.0665 (7)
C9	0.9756 (3)	0.5314 (3)	0.1862 (2)	0.0659 (6)
H9A	0.935350	0.438646	0.133610	0.079*
C10	0.9115 (3)	0.5229 (3)	0.28380 (19)	0.0592 (6)
H10A	0.827792	0.422230	0.298028	0.071*
C11	0.6893 (9)	0.7289 (7)	0.8505 (5)	0.0447 (13)	0.503 (4)
C12	0.5575 (7)	0.6983 (7)	0.9197 (5)	0.0691 (15)	0.503 (4)
H12A	0.439229	0.635805	0.894732	0.083*	0.503 (4)
C13	0.6019 (12)	0.7611 (13)	1.0269 (6)	0.074 (2)	0.503 (4)
H13A	0.513251	0.739287	1.073481	0.089*	0.503 (4)
C14	0.7747 (12)	0.8546 (10)	1.0639 (5)	0.0740 (16)	0.503 (4)
H14A	0.804349	0.898834	1.135130	0.089*	0.503 (4)
C15	0.9041 (8)	0.8822 (8)	0.9946 (4)	0.0811 (17)	0.503 (4)
H15A	1.022734	0.943608	1.019215	0.097*	0.503 (4)
C16	0.8600 (7)	0.8201 (7)	0.8893 (4)	0.0660 (14)	0.503 (4)
H16A	0.949586	0.841027	0.843322	0.079*	0.503 (4)
C11'	0.5982 (9)	0.7008 (8)	0.8494 (5)	0.0489 (14)	0.497 (4)
C12'	0.5168 (7)	0.8137 (6)	0.8805 (4)	0.0631 (13)	0.497 (4)
H12B	0.447047	0.841350	0.831371	0.076*	0.497 (4)
C13'	0.5408 (8)	0.8852 (7)	0.9865 (5)	0.0759 (18)	0.497 (4)
H13B	0.488252	0.962201	1.007970	0.091*	0.497 (4)
C14'	0.6390 (15)	0.8437 (12)	1.0570 (7)	0.079 (3)	0.497 (4)
H14B	0.655646	0.893516	1.127240	0.094*	0.497 (4)
C15'	0.7133 (14)	0.7321 (12)	1.0286 (5)	0.0843 (19)	0.497 (4)
H15B	0.779040	0.702274	1.078940	0.101*	0.497 (4)
C16'	0.6923 (8)	0.6598 (8)	0.9226 (5)	0.0793 (17)	0.497 (4)
H16B	0.744737	0.582013	0.902974	0.095*	0.497 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0842 (2)	0.05494 (16)	0.05450 (16)	−0.00131 (12)	0.02403 (12)	−0.00748 (11)
S1	0.0911 (4)	0.0681 (4)	0.0419 (3)	0.0401 (3)	0.0203 (3)	0.0126 (3)
F1	0.1003 (12)	0.1287 (15)	0.0746 (10)	0.0375 (11)	0.0439 (9)	0.0375 (10)
N1	0.0588 (10)	0.0484 (10)	0.0428 (9)	0.0154 (9)	0.0093 (8)	0.0067 (8)
C1	0.1015 (19)	0.0518 (13)	0.0448 (12)	0.0257 (13)	−0.0005 (12)	−0.0010 (10)
N2	0.0706 (12)	0.0494 (10)	0.0385 (9)	0.0183 (9)	0.0088 (8)	0.0032 (8)
C2	0.145 (3)	0.0759 (18)	0.0422 (13)	0.0652 (19)	0.0157 (15)	0.0117 (12)
N3	0.0696 (11)	0.0478 (10)	0.0492 (10)	0.0162 (9)	0.0199 (9)	0.0087 (8)
C3	0.0593 (12)	0.0513 (12)	0.0400 (10)	0.0240 (10)	0.0079 (9)	0.0079 (9)
C4	0.0643 (14)	0.0516 (13)	0.0492 (12)	0.0108 (11)	0.0016 (10)	0.0044 (10)
C5	0.0504 (12)	0.0514 (12)	0.0535 (12)	0.0119 (10)	0.0028 (10)	0.0139 (10)
C6	0.0733 (16)	0.0558 (14)	0.0663 (15)	0.0074 (12)	0.0053 (13)	0.0159 (12)
C7	0.0708 (16)	0.0692 (17)	0.0845 (19)	0.0101 (13)	0.0177 (14)	0.0362 (16)
C8	0.0585 (14)	0.0891 (19)	0.0617 (15)	0.0311 (14)	0.0196 (12)	0.0303 (14)
C9	0.0575 (14)	0.0732 (16)	0.0636 (15)	0.0204 (12)	0.0141 (11)	0.0049 (12)
C10	0.0515 (12)	0.0560 (13)	0.0627 (14)	0.0092 (10)	0.0148 (11)	0.0103 (11)
C11	0.052 (3)	0.043 (3)	0.043 (3)	0.018 (3)	0.015 (3)	0.012 (2)
C12	0.060 (3)	0.084 (4)	0.059 (4)	0.021 (3)	0.014 (3)	0.005 (3)
C13	0.084 (6)	0.101 (6)	0.045 (4)	0.042 (5)	0.018 (4)	0.009 (4)
C14	0.100 (5)	0.083 (5)	0.042 (3)	0.038 (4)	0.006 (3)	0.001 (3)
C15	0.085 (4)	0.096 (4)	0.055 (3)	0.029 (3)	0.003 (3)	0.001 (3)
C16	0.066 (3)	0.077 (3)	0.049 (3)	0.020 (3)	0.011 (2)	0.003 (2)
C11'	0.051 (4)	0.053 (3)	0.036 (3)	0.009 (3)	0.016 (3)	0.007 (2)
C12'	0.066 (3)	0.058 (3)	0.065 (3)	0.019 (2)	0.009 (2)	0.020 (2)
C13'	0.092 (4)	0.057 (3)	0.083 (4)	0.031 (3)	0.041 (3)	0.006 (3)
C14'	0.095 (7)	0.073 (5)	0.042 (4)	0.002 (5)	0.013 (4)	−0.004 (3)
C15'	0.087 (5)	0.111 (7)	0.055 (4)	0.037 (5)	−0.011 (3)	0.012 (4)
C16'	0.084 (4)	0.096 (4)	0.072 (4)	0.053 (4)	0.008 (3)	0.002 (3)

Geometric parameters (Å, º) top

S1—C3	1.720 (2)	C9—C10	1.369 (3)
S1—C2	1.848 (3)	C9—H9A	0.9300
F1—C8	1.353 (3)	C10—H10A	0.9300
N1—C4	1.276 (3)	C11—C16	1.353 (8)
N1—N2	1.380 (2)	C11—C12	1.383 (7)
C1—N2	1.465 (3)	C12—C13	1.393 (10)
C1—C2	1.506 (4)	C12—H12A	0.9300
C1—H1A	0.9700	C13—C14	1.364 (14)
C1—H1B	0.9700	C13—H13A	0.9300
N2—C3	1.339 (3)	C14—C15	1.370 (9)
C2—C11'	1.505 (6)	C14—H14A	0.9300
C2—C11	1.607 (7)	C15—C16	1.370 (7)
C2—H2A	0.9800	C15—H15A	0.9300
N3—C3	1.297 (3)	C16—H16A	0.9300
N3—H3A	0.9001	C11'—C16'	1.333 (9)
N3—H3B	0.9000	C11'—C12'	1.389 (8)
C4—C5	1.458 (3)	C12'—C13'	1.394 (8)
C4—H4A	0.9300	C12'—H12B	0.9300
C5—C6	1.386 (3)	C13'—C14'	1.334 (12)
C5—C10	1.390 (3)	C13'—H13B	0.9300
C6—C7	1.379 (4)	C14'—C15'	1.329 (15)
C6—H6A	0.9300	C14'—H14B	0.9300
C7—C8	1.358 (4)	C15'—C16'	1.399 (9)
C7—H7A	0.9300	C15'—H15B	0.9300
C8—C9	1.373 (4)	C16'—H16B	0.9300

C3—S1—C2	90.65 (11)	C10—C9—H9A	121.0
C4—N1—N2	117.98 (19)	C8—C9—H9A	121.0
N2—C1—C2	105.8 (2)	C9—C10—C5	121.2 (2)
N2—C1—H1A	110.6	C9—C10—H10A	119.4
C2—C1—H1A	110.6	C5—C10—H10A	119.4
N2—C1—H1B	110.6	C16—C11—C12	118.7 (5)
C2—C1—H1B	110.6	C16—C11—C2	133.2 (5)
H1A—C1—H1B	108.7	C12—C11—C2	108.2 (5)
C3—N2—N1	116.37 (17)	C11—C12—C13	120.0 (6)
C3—N2—C1	115.67 (18)	C11—C12—H12A	120.0
N1—N2—C1	127.52 (19)	C13—C12—H12A	120.0
C11'—C2—C1	129.4 (4)	C14—C13—C12	120.3 (7)
C1—C2—C11	104.7 (3)	C14—C13—H13A	119.8
C11'—C2—S1	104.9 (3)	C12—C13—H13A	119.8
C1—C2—S1	105.04 (17)	C13—C14—C15	119.0 (6)
C11—C2—S1	112.7 (2)	C13—C14—H14A	120.5
C1—C2—H2A	111.4	C15—C14—H14A	120.5
C11—C2—H2A	111.4	C16—C15—C14	120.5 (6)
S1—C2—H2A	111.4	C16—C15—H15A	119.7
C3—N3—H3A	117.3	C14—C15—H15A	119.7
C3—N3—H3B	119.6	C11—C16—C15	121.5 (5)
H3A—N3—H3B	120.5	C11—C16—H16A	119.2
N3—C3—N2	123.59 (19)	C15—C16—H16A	119.2
N3—C3—S1	123.18 (17)	C16'—C11'—C12'	118.8 (6)
N2—C3—S1	113.23 (16)	C16'—C11'—C2	119.7 (5)
N1—C4—C5	120.0 (2)	C12'—C11'—C2	121.2 (5)
N1—C4—H4A	120.0	C11'—C12'—C13'	119.1 (5)
C5—C4—H4A	120.0	C11'—C12'—H12B	120.4
C6—C5—C10	118.6 (2)	C13'—C12'—H12B	120.4
C6—C5—C4	119.1 (2)	C14'—C13'—C12'	120.3 (6)
C10—C5—C4	122.3 (2)	C14'—C13'—H13B	119.9
C7—C6—C5	120.8 (3)	C12'—C13'—H13B	119.9
C7—C6—H6A	119.6	C15'—C14'—C13'	121.0 (8)
C5—C6—H6A	119.6	C15'—C14'—H14B	119.5
C8—C7—C6	118.3 (2)	C13'—C14'—H14B	119.5
C8—C7—H7A	120.9	C14'—C15'—C16'	119.7 (8)
C6—C7—H7A	120.9	C14'—C15'—H15B	120.1
F1—C8—C7	119.0 (2)	C16'—C15'—H15B	120.1
F1—C8—C9	117.9 (3)	C11'—C16'—C15'	121.0 (6)
C7—C8—C9	123.1 (2)	C11'—C16'—H16B	119.5
C10—C9—C8	118.0 (3)	C15'—C16'—H16B	119.5

C4—N1—N2—C3	−169.1 (2)	C6—C5—C10—C9	−2.0 (4)
C4—N1—N2—C1	3.0 (3)	C4—C5—C10—C9	176.7 (2)
C2—C1—N2—C3	−26.1 (3)	C1—C2—C11—C16	−1.1 (7)
C2—C1—N2—N1	161.8 (2)	S1—C2—C11—C16	112.5 (6)
N2—C1—C2—C11'	155.8 (4)	C1—C2—C11—C12	−179.8 (4)
N2—C1—C2—C11	150.2 (3)	S1—C2—C11—C12	−66.2 (5)
N2—C1—C2—S1	31.4 (2)	C16—C11—C12—C13	0.1 (10)
C3—S1—C2—C11'	−163.6 (3)	C2—C11—C12—C13	178.9 (6)
C3—S1—C2—C1	−24.92 (19)	C11—C12—C13—C14	0.8 (14)
C3—S1—C2—C11	−138.3 (3)	C12—C13—C14—C15	−1.5 (15)
N1—N2—C3—N3	−0.7 (3)	C13—C14—C15—C16	1.4 (12)
C1—N2—C3—N3	−173.7 (2)	C12—C11—C16—C15	−0.2 (9)
N1—N2—C3—S1	179.87 (14)	C2—C11—C16—C15	−178.7 (5)
C1—N2—C3—S1	6.8 (3)	C14—C15—C16—C11	−0.6 (10)
C2—S1—C3—N3	−168.1 (2)	C1—C2—C11'—C16'	−64.5 (7)
C2—S1—C3—N2	11.35 (19)	S1—C2—C11'—C16'	59.9 (7)
N2—N1—C4—C5	−177.36 (19)	C1—C2—C11'—C12'	109.3 (6)
N1—C4—C5—C6	174.4 (2)	S1—C2—C11'—C12'	−126.3 (5)
N1—C4—C5—C10	−4.2 (4)	C16'—C11'—C12'—C13'	2.2 (9)
C10—C5—C6—C7	0.8 (4)	C2—C11'—C12'—C13'	−171.6 (5)
C4—C5—C6—C7	−177.9 (2)	C11'—C12'—C13'—C14'	−0.9 (9)
C5—C6—C7—C8	1.2 (4)	C12'—C13'—C14'—C15'	−1.0 (13)
C6—C7—C8—F1	179.3 (2)	C13'—C14'—C15'—C16'	1.5 (16)
C6—C7—C8—C9	−2.3 (4)	C12'—C11'—C16'—C15'	−1.7 (11)
F1—C8—C9—C10	179.6 (2)	C2—C11'—C16'—C15'	172.2 (6)
C7—C8—C9—C10	1.1 (4)	C14'—C15'—C16'—C11'	−0.2 (14)
C8—C9—C10—C5	1.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Br1	0.90	2.36	3.2557 (18)	172
N3—H3B···Br1ⁱ	0.90	2.55	3.3552 (18)	150
C4—H4A···Br1ⁱⁱ	0.93	2.99	3.726 (2)	137

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

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

Contact	Percentage contribution
H···H	44.3
Br···H/H···Br	16.8
C···H/H···C	13.9
F···H/H···F	10.3
S···H/H···S	3.8
N···C/C···N	3.6
S···C/C···S	2.7
N···H/H···N	1.8
C···C	1.5
N···N	0.7
Br···C/C···Br	0.3
S···N/N···S	0.3
F···C/C···F	0.2

Acknowledgements

Ali Khalilov is grateful to Baku State University for the `50+50' individual grant in support of this work.

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