Crystal structure and Hirshfeld surface analysis of (E)-5-phenyl-3-[(pyridin-4-yl­methyl­idene)amino]­thia­zolidin-2-iminium bromide monohydrate

Akkurt, M.; Maharramov, A.M.; Duruskari, G.S.; Toze, F.A.A.; Khalilov, A.N.

doi:10.1107/S2056989018011155

research communications

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ISSN: 2056-9890

Volume 74| Part 9| September 2018| Pages 1290-1294

https://doi.org/10.1107/S2056989018011155

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Crystal structure and Hirshfeld surface analysis of (E)-5-phenyl-3-[(pyridin-4-ylmethylidene)amino]thiazolidin-2-iminium bromide monohydrate

Mehmet Akkurt,^a Abel M. Maharramov,^b Gulnara Sh. Duruskari,^b Flavien A. A. Toze ^c ^* and Ali N. Khalilov ^b

^aDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^bOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az, 1148 Baku, Azerbaijan, and ^cDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of Cameroon
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 27 July 2018; accepted 4 August 2018; online 21 August 2018)

In the cation of the title salt, C₁₅H₁₅N₄S⁺·Br⁻·H₂O, the central thiazolidine ring adopts an envelope conformation with puckering parameters Q(2) = 0.279 (4) Å and φ(2) = 222.5 (9)°. The mean plane of the thiazolidine ring makes dihedral angles of 12.4 (2) and 66.8 (3)° with the pyridine and phenyl rings, respectively. The pyridine ring in the title molecule is essentially planar (r.m.s deviation = 0.005 Å). In the crystal, the cations, anions and water molecules are linked into a three-dimensional network, which forms cross layers parallel to the (120) and ( $[\overline{1}]$ 20) planes via O—H⋯Br, N—H⋯Br and N—H⋯N hydrogen bonds. C—H⋯π interactions also help in the stabilization of the molecular packing. Hirshfeld surface analysis and 2D (two-dimensional) fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (35.5%), C⋯H/H⋯C (23.9%), Br⋯H/H⋯Br (16.4%), N⋯H/H⋯N (10.6%) and S⋯H/H⋯S (7.9%) interactions.

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

CCDC reference: 1837127

1. Chemical context

Schiff bases and related hydrazone compounds play an important role in coordination and medicinal chemistry due to their high coordination ability (Mahmoudi et al., 2017a ,b ,c ; Mitoraj et al., 2018 ; Shixaliyev et al., 2013a ), application of those metal complexes in catalysis (Jlassi et al., 2014 ; Gurbanov et al., 2018 ; Mahmudov et al., 2014 ; Shixaliyev et al., 2013b , 2014 ), biological properties (Abedi et al., 2014 ), etc. Inter- and intramolecular weak interactions may also effect their properties (Mahmudov et al., 2016 , 2017a ,b ). Herein we found strong O—H⋯Br⁻ and N⁺—H⋯Br⁻ types of charge-assisted hydrogen bonds in (E)-5-phenyl-3-[(pyridin-4-ylmethylidene)amino]thiazolidin-2-iminium bromide monohydrate.

2. Structural commentary

The thiazolidine ring (atoms S1/C1–C4) in the cation of the title salt (Fig. 1) adopts an envelope conformation with the puckering parameters (Cremer & Pople, 1975 ) Q(2) = 0.279 (4) Å and φ(2) = 222.5 (9)°. The mean plane of the thiazolidine ring makes dihedral angles of 12.4 (2) and 66.8 (3)° with the pyridine (N4/C5–C9) and phenyl (C10–C15) rings, respectively. The pyridine ring of the title molecule is essentially planar (r.m.s deviation = 0.005 Å). The N2—N1—C4—C5 bridge that links the thiazolidine and 2,3-dichlorobenzene rings has a torsion angle of 178.3 (4)°.

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.

3. Supramolecular features and Hirshfeld surface analysis

As shown in Figs. 2 and 3, in the crystal, the cations, anions and water molecules are linked into a three-dimensional network, which forms cross layers parallel to the (120) and ( $[\overline{1}]$ 20) planes via O—H⋯Br, N—H⋯Br and N—H⋯N hydrogen bonds (Table 1). Furthermore, C—H⋯π interactions also help in the stabilization of the molecular packing (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the N4/C5–C9 pyridine and C10–C15 phenyl ring, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1C⋯Br1	0.95	2.39	3.333 (4)	169
O1—H1D⋯Br1ⁱ	0.95	2.56	3.427 (5)	152
N3—H3A⋯Br1ⁱⁱ	0.90	2.45	3.333 (4)	167
N3—H3B⋯N4ⁱⁱⁱ	0.90	1.99	2.840 (6)	158
C9—H9A⋯Cg2ⁱⁱⁱ	0.93	2.96	3.650 (5)	132
C12—H12A⋯Cg3^iv	0.93	2.82	3.565 (8)	137
C15—H15A⋯Cg3^v	0.93	2.80	3.548 (6)	135
Symmetry codes: (i) x+1, y, z; (ii) x, y-1, z; (iii) $[-x+2, y-{\script{1\over 2}}, -z+2]$ ; (iv) $[-x+2, y-{\script{1\over 2}}, -z+1]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Figure 2
A view of the intermolecular hydrogen bonds of the title compound along the a axis.

Figure 3
A view of the packing and intermolecular hydrogen bonding of the title compound along the c axis.

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 (two-dimensional) 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 −0.5782 (red) to 1.2417 a.u. (blue) is shown in Fig. 4. This plot was generated to quantify and visualize the intermolecular interactions and to explain the observed crystal packing. The dark-red spots on the d_norm surface arise as a result of short interatomic contacts, while the other weaker intermolecular interactions appear as light-red spots.

Figure 4
Hirshfeld surface of the title compound mapped over d_norm.

Fig. 5(a) shows the 2D fingerprint plot of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode. These represent both the overall two-dimensional fingerprint plots and those that represent H⋯H, C⋯H/H⋯C, Br⋯H/H⋯Br, N⋯H/H⋯N and S⋯H/H⋯S contacts, respectively (Figs. 5b–f). The most significant intermolecular interactions are the H⋯H interactions (35.5%) (Fig. 5b). The reciprocal C⋯H/H⋯C interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.7 Å and contribute 23.9% to the Hirshfeld surface (Fig. 5c). The reciprocal Br⋯H/H⋯Br, N⋯H/H⋯N and S⋯H/H⋯S interactions with 16.4, 10.6 and 7.9% contributions are present as sharp symmetrical spikes at diagonal axes d_e + d_i ≃ 2.3, 2.9 and 2.8 Å, respectively (Figs. 5d–f). Furthermore, there are O⋯H/H⋯O (2.8%), Br⋯C/C⋯Br (1.1%), Br⋯N/N⋯Br (1.0%), Br⋯S/S⋯Br (0.6%), N⋯C/C⋯N (0.3%) and N⋯N (0.1%) contacts (Table 2).

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

Contact	Percentage contribution
H⋯H	35.5
C⋯H/H⋯C	23.9
Br⋯H/H⋯Br	16.4
N⋯H/H⋯N	10.6
S⋯H/H⋯S	7.9
Br⋯C/C⋯Br	1.1
Br⋯N/N⋯Br	1.0
Br⋯S/S⋯Br	0.6
C⋯N/N⋯C	0.3
N⋯N/N⋯N	0.1

Figure 5
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) Br⋯H/H⋯Br, (e) N⋯H/H⋯N 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].

4. Database survey

In a recent article of ours, which on the crystal structure of (E)-3-[(2,3-dichlorobenzylidene)amino]-5-phenylthiazolidin-2-iminium bromide (Akkurt et al., 2018 ), the 3-N atom of the cation carries an N substituent, as found in the title compound. In the crystal, 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 and inversion-related Cl⋯Cl halogen bonds and C—Cl⋯π(ring) contacts also contribute to the molecular packing.

In addition, a search of the Cambridge Structural Database (CSD Version 5.39, November 2017 + 3 updates; Groom et al., 2016 ) yielded six hits for 2-thiazolidiniminium compounds, with four of them reporting essentially the same cation [CSD refcodes 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 all cases, the 3-N atom carries a C substituent not N 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.

5. Synthesis and crystallization

To the solution of 1 mmol of 3-amino-5-phenylthiazolidin-2-iminium bromide in 20 ml ethanol was added 1 mmol of isonicotinaldehyde and the solution was refluxed for 2 h. The reaction mixture was then cooled. Reaction products were precipitated from the reaction mixture as colourless single crystals, collected by filtration and washed with cold acetone.

Yield: 57%; m.p.: 496 K. Analysis calculated for C₁₅H₁₅BrN₄S: C 49.59, H 4.16, N 15.42%; found: C 49.52, H 4.11, N 15.35%. ¹H NMR (300 MHz, DMSO-d₆) : δ 4.57 (q, 1H, CH₂, ³J_H–H = 6.6 Hz), 4.89 (t, 1H, CH₂, ³J_H–H = 8.1 Hz), 5.62 (t, 1H, CH-Ar, ³J_H–H = 7.5 Hz), 7.37–7.57 (m, 5H, 5 Ar-H), 8.015–7.998 (d, 2H, 2CH_arom, ³J_H–H = 5.1 Hz), 8.46 (s, 1H, CH=), 8.728–8.711 (d, 2H, 2CH_arom, ³J_H–H = 5.1 Hz), 10.52 (s, 2H, NH₂=). ¹³C NMR (75MHz, DMSO-d₆): δ 45.54, 56.00, 122.17, 127.86, 128.98, 129.16, 137.43, 140.16, 148.88, 150.31, 168.98. MS (ESI), m/z: 283.36 [C₁₅H₁₅N₄S]⁺ and 79.88 Br⁻.

6. 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 O—H = 0.95 Å, N—H = 0.90 Å and C—H = 0.93–0.98 Å, and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O) for the H atoms of the water molecule.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₄S⁺·Br⁻·H₂O
M_r	381.30
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	5.8515 (8), 7.5304 (10), 18.859 (3)
β (°)	93.979 (5)
V (Å³)	829.0 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.61
Crystal size (mm)	0.19 × 0.15 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.623, 0.698
No. of measured, independent and observed [I > 2σ(I)] reflections	12061, 3373, 3107
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.087, 1.08
No. of reflections	3373
No. of parameters	199
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.47
Absolute structure	Flack x determined using 1291 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.004 (8)
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1837127

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018011155/xu5936sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018011155/xu5936Isup2.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, 2009).

(E)-5-Phenyl-3-[(pyridin-4-ylmethylidene)amino]thiazolidin-2-iminium bromide monohydrate top

Crystal data top

C₁₅H₁₅N₄S⁺·Br⁻·H₂O	F(000) = 388
M_r = 381.30	D_x = 1.527 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 5.8515 (8) Å	Cell parameters from 6867 reflections
b = 7.5304 (10) Å	θ = 2.9–26.4°
c = 18.859 (3) Å	µ = 2.61 mm⁻¹
β = 93.979 (5)°	T = 296 K
V = 829.0 (2) Å³	Block, colorless
Z = 2	0.19 × 0.15 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	3107 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.076
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θ_max = 26.4°, θ_min = 2.9°
T_min = 0.623, T_max = 0.698	h = −7→7
12061 measured reflections	k = −9→9
3373 independent reflections	l = −21→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0256P)² + 0.6286P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3373 reflections	Δρ_max = 0.49 e Å⁻³
199 parameters	Δρ_min = −0.47 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1291 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (8)

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	0.00107 (9)	0.87805 (8)	0.76086 (3)	0.05140 (19)
O1	0.4881 (7)	0.6571 (7)	0.7445 (3)	0.0670 (13)
H1D	0.619040	0.714648	0.766487	0.100*
H1C	0.362040	0.733228	0.751357	0.100*
S1	0.4339 (2)	0.15399 (19)	0.67953 (6)	0.0382 (3)
N1	0.8263 (6)	0.3319 (5)	0.8366 (2)	0.0295 (9)
N2	0.7239 (7)	0.2983 (5)	0.7699 (2)	0.0303 (8)
N3	0.4501 (6)	0.1215 (6)	0.8202 (2)	0.0355 (9)
H3A	0.328282	0.049581	0.812009	0.043*
H3B	0.512382	0.129791	0.865099	0.043*
N4	1.3503 (8)	0.5477 (6)	1.0413 (2)	0.0411 (10)
C1	0.8150 (8)	0.3485 (7)	0.7026 (2)	0.0355 (11)
H1A	0.942871	0.272508	0.692765	0.043*
H1B	0.867805	0.470588	0.704580	0.043*
C2	0.6215 (9)	0.3270 (6)	0.6453 (3)	0.0367 (11)
H2A	0.535751	0.438691	0.640770	0.044*
C3	0.5413 (7)	0.1933 (6)	0.7656 (2)	0.0280 (9)
C4	1.0129 (8)	0.4175 (6)	0.8403 (3)	0.0342 (11)
H4A	1.078821	0.452819	0.799119	0.041*
C5	1.1255 (8)	0.4610 (6)	0.9111 (2)	0.0303 (9)
C6	1.3363 (9)	0.5471 (7)	0.9143 (3)	0.0399 (12)
H6A	1.405181	0.577708	0.872999	0.048*
C7	1.4407 (9)	0.5859 (8)	0.9808 (3)	0.0415 (12)
H7A	1.582539	0.642081	0.982961	0.050*
C8	1.1475 (10)	0.4651 (8)	1.0373 (3)	0.0421 (12)
H8A	1.081980	0.437142	1.079457	0.051*
C9	1.0312 (8)	0.4194 (6)	0.9743 (3)	0.0349 (11)
H9A	0.890877	0.361247	0.974094	0.042*
C10	0.6939 (9)	0.2728 (7)	0.5720 (3)	0.0354 (11)
C11	0.8870 (10)	0.1764 (8)	0.5602 (3)	0.0501 (14)
H11A	0.977907	0.131751	0.598504	0.060*
C12	0.9462 (10)	0.1458 (11)	0.4924 (5)	0.064 (2)
H12A	1.081948	0.086515	0.485002	0.077*
C13	0.8064 (13)	0.2022 (10)	0.4350 (3)	0.0626 (19)
H13A	0.846758	0.180147	0.389002	0.075*
C14	0.6057 (15)	0.2916 (9)	0.4462 (3)	0.0610 (19)
H14A	0.508677	0.327949	0.407801	0.073*
C15	0.5505 (11)	0.3266 (7)	0.5146 (3)	0.0450 (13)
H15A	0.415794	0.386965	0.522268	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0357 (2)	0.0535 (3)	0.0647 (4)	0.0010 (3)	0.0019 (2)	−0.0076 (4)
O1	0.059 (3)	0.059 (3)	0.084 (4)	0.016 (3)	0.013 (2)	−0.008 (3)
S1	0.0326 (5)	0.0560 (8)	0.0249 (5)	−0.0080 (6)	−0.0050 (4)	−0.0042 (5)
N1	0.0331 (19)	0.029 (2)	0.0250 (18)	−0.0004 (14)	−0.0079 (14)	−0.0049 (13)
N2	0.0325 (19)	0.0329 (19)	0.0245 (19)	−0.0024 (16)	−0.0055 (15)	−0.0013 (15)
N3	0.0296 (18)	0.051 (3)	0.0252 (19)	−0.0036 (19)	−0.0033 (15)	0.0017 (18)
N4	0.043 (2)	0.043 (3)	0.036 (2)	0.003 (2)	−0.0098 (18)	−0.0099 (19)
C1	0.037 (2)	0.042 (3)	0.028 (2)	−0.002 (2)	−0.0003 (17)	−0.001 (2)
C2	0.040 (2)	0.034 (3)	0.035 (3)	0.0068 (19)	−0.002 (2)	−0.0006 (18)
C3	0.0238 (19)	0.031 (2)	0.028 (2)	0.0050 (18)	−0.0030 (16)	−0.0005 (18)
C4	0.038 (2)	0.037 (3)	0.027 (2)	−0.0021 (19)	−0.0028 (18)	−0.0039 (18)
C5	0.032 (2)	0.030 (2)	0.029 (2)	−0.0017 (18)	−0.0043 (18)	−0.0047 (18)
C6	0.039 (3)	0.046 (3)	0.034 (3)	−0.009 (2)	0.000 (2)	−0.006 (2)
C7	0.031 (2)	0.047 (3)	0.045 (3)	−0.003 (2)	−0.009 (2)	−0.011 (2)
C8	0.050 (3)	0.047 (3)	0.030 (3)	0.000 (2)	0.004 (2)	−0.004 (2)
C9	0.033 (2)	0.037 (3)	0.035 (2)	−0.0021 (18)	−0.0004 (18)	−0.0032 (18)
C10	0.038 (2)	0.040 (3)	0.027 (2)	−0.007 (2)	−0.0022 (19)	0.0002 (19)
C11	0.044 (3)	0.048 (3)	0.056 (3)	0.005 (3)	−0.014 (3)	−0.007 (3)
C12	0.045 (3)	0.067 (4)	0.084 (5)	−0.005 (4)	0.018 (3)	−0.031 (4)
C13	0.093 (5)	0.061 (4)	0.036 (3)	−0.017 (4)	0.026 (3)	−0.010 (3)
C14	0.103 (6)	0.045 (3)	0.032 (3)	−0.007 (4)	−0.019 (3)	0.012 (2)
C15	0.051 (3)	0.037 (3)	0.046 (3)	0.006 (2)	−0.005 (2)	−0.003 (2)

Geometric parameters (Å, º) top

O1—H1D	0.9500	C5—C9	1.384 (7)
O1—H1C	0.9500	C5—C6	1.391 (7)
S1—C3	1.725 (4)	C6—C7	1.389 (7)
S1—C2	1.848 (5)	C6—H6A	0.9300
N1—C4	1.266 (6)	C7—H7A	0.9300
N1—N2	1.380 (5)	C8—C9	1.372 (7)
N2—C3	1.327 (6)	C8—H8A	0.9300
N2—C1	1.459 (6)	C9—H9A	0.9300
N3—C3	1.310 (6)	C10—C11	1.374 (8)
N3—H3A	0.9000	C10—C15	1.384 (7)
N3—H3B	0.9000	C11—C12	1.367 (10)
N4—C7	1.322 (8)	C11—H11A	0.9300
N4—C8	1.337 (8)	C12—C13	1.378 (11)
C1—C2	1.519 (6)	C12—H12A	0.9300
C1—H1A	0.9700	C13—C14	1.383 (11)
C1—H1B	0.9700	C13—H13A	0.9300
C2—C10	1.529 (7)	C14—C15	1.376 (9)
C2—H2A	0.9800	C14—H14A	0.9300
C4—C5	1.484 (6)	C15—H15A	0.9300
C4—H4A	0.9300

H1D—O1—H1C	106.0	C7—C6—C5	118.0 (5)
C3—S1—C2	91.2 (2)	C7—C6—H6A	121.0
C4—N1—N2	117.6 (4)	C5—C6—H6A	121.0
C3—N2—N1	117.5 (4)	N4—C7—C6	123.8 (5)
C3—N2—C1	116.3 (4)	N4—C7—H7A	118.1
N1—N2—C1	125.7 (4)	C6—C7—H7A	118.1
C3—N3—H3A	118.3	N4—C8—C9	123.4 (5)
C3—N3—H3B	123.4	N4—C8—H8A	118.3
H3A—N3—H3B	117.9	C9—C8—H8A	118.3
C7—N4—C8	117.3 (4)	C8—C9—C5	119.0 (5)
N2—C1—C2	106.9 (4)	C8—C9—H9A	120.5
N2—C1—H1A	110.3	C5—C9—H9A	120.5
C2—C1—H1A	110.3	C11—C10—C15	119.2 (5)
N2—C1—H1B	110.3	C11—C10—C2	124.8 (5)
C2—C1—H1B	110.3	C15—C10—C2	116.0 (5)
H1A—C1—H1B	108.6	C12—C11—C10	120.4 (6)
C1—C2—C10	115.6 (4)	C12—C11—H11A	119.8
C1—C2—S1	104.9 (3)	C10—C11—H11A	119.8
C10—C2—S1	109.6 (3)	C11—C12—C13	120.5 (6)
C1—C2—H2A	108.8	C11—C12—H12A	119.8
C10—C2—H2A	108.8	C13—C12—H12A	119.8
S1—C2—H2A	108.8	C12—C13—C14	119.6 (6)
N3—C3—N2	124.7 (4)	C12—C13—H13A	120.2
N3—C3—S1	121.8 (4)	C14—C13—H13A	120.2
N2—C3—S1	113.5 (3)	C15—C14—C13	119.6 (6)
N1—C4—C5	119.3 (4)	C15—C14—H14A	120.2
N1—C4—H4A	120.3	C13—C14—H14A	120.2
C5—C4—H4A	120.3	C14—C15—C10	120.5 (6)
C9—C5—C6	118.3 (4)	C14—C15—H15A	119.7
C9—C5—C4	123.1 (4)	C10—C15—H15A	119.7
C6—C5—C4	118.6 (4)

C4—N1—N2—C3	173.3 (4)	C8—N4—C7—C6	0.8 (8)
C4—N1—N2—C1	1.8 (7)	C5—C6—C7—N4	−0.8 (9)
C3—N2—C1—C2	22.4 (6)	C7—N4—C8—C9	−0.1 (8)
N1—N2—C1—C2	−166.1 (4)	N4—C8—C9—C5	−0.4 (8)
N2—C1—C2—C10	−148.0 (4)	C6—C5—C9—C8	0.3 (7)
N2—C1—C2—S1	−27.1 (5)	C4—C5—C9—C8	−179.9 (5)
C3—S1—C2—C1	21.6 (3)	C1—C2—C10—C11	27.7 (7)
C3—S1—C2—C10	146.3 (4)	S1—C2—C10—C11	−90.6 (6)
N1—N2—C3—N3	0.9 (7)	C1—C2—C10—C15	−152.3 (5)
C1—N2—C3—N3	173.2 (5)	S1—C2—C10—C15	89.3 (5)
N1—N2—C3—S1	−177.7 (3)	C15—C10—C11—C12	5.0 (9)
C1—N2—C3—S1	−5.5 (5)	C2—C10—C11—C12	−175.1 (6)
C2—S1—C3—N3	171.0 (4)	C10—C11—C12—C13	−3.8 (11)
C2—S1—C3—N2	−10.3 (4)	C11—C12—C13—C14	0.6 (11)
N2—N1—C4—C5	178.3 (4)	C12—C13—C14—C15	1.4 (10)
N1—C4—C5—C9	−3.0 (7)	C13—C14—C15—C10	−0.1 (9)
N1—C4—C5—C6	176.7 (5)	C11—C10—C15—C14	−3.1 (9)
C9—C5—C6—C7	0.2 (8)	C2—C10—C15—C14	177.0 (5)
C4—C5—C6—C7	−179.6 (5)

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of the N4/C5–C9 pyridine and the C10–C15 phenyl ring, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···Br1	0.95	2.39	3.333 (4)	169
O1—H1D···Br1ⁱ	0.95	2.56	3.427 (5)	152
N3—H3A···Br1ⁱⁱ	0.90	2.45	3.333 (4)	167
N3—H3B···N4ⁱⁱⁱ	0.90	1.99	2.840 (6)	158
C9—H9A···Cg2ⁱⁱⁱ	0.93	2.96	3.650 (5)	132
C12—H12A···Cg3^iv	0.93	2.82	3.565 (8)	137
C15—H15A···Cg3^v	0.93	2.80	3.548 (6)	135

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

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

Contact	Percentage contribution
H···H	35.5
C···H/H···C	23.9
Br···H/H···Br	16.4
N···H/H···N	10.6
S···H/H···S	7.9
Br..C/C···Br	1.1
Br..N/N···Br	1.0
Br..S/S···Br	0.6
C..N/N···C	0.3
N..N/N···N	0.1

Acknowledgements

This work has been partially supported by Baku State University.

References

Abedi, M., Khandar, A. A., Gargari, M. S., Gurbanov, A. V., Hosseini, S. A. & Mahmoudi, G. (2014). Z. Anorg. Allg. Chem. 640, 2193–2197. CrossRef Google Scholar
Akkurt, M., Duruskari, G. S., Toze, F. A. A., Khalilov, A. N. & Huseynova, A. T. (2018). Acta Cryst. E74, 1168–1172. CrossRef IUCr Journals Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS 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 CSD CrossRef IUCr Journals Google Scholar
Gurbanov, A. V., Huseynov, F. E., Mahmoudi, G., Maharramov, A. M., Guedes da Silva, M. F. C., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Inorg. Chim. Acta, 469, 197–201. CrossRef Google Scholar
Jlassi, R., Ribeiro, A. P. C., Guedes da Silva, M. F. C., Mahmudov, K. T., Kopylovich, M. N., Anisimova, T. B., Naïli, H., Tiago, G. A. O. & Pombeiro, A. J. L. (2014). Eur. J. Inorg. Chem. pp. 45410–4550. Google Scholar
Mahmoudi, G., Dey, L., Chowdhury, H., Bauza, A., Ghosh, B. K., Kirillov, A. M., Seth, S. K., Gurbanov, A. V. & Frontera, A. (2017a). Inorg. Chim. Acta, 461, 192–205. CrossRef Google Scholar
Mahmoudi, G., Gurbanov, A. V., Rodriguez-Hermida, S., Carballo, R., Amini, M., Bacchi, A., Mitoraj, M. P., Sagan, F., Kukulka, M. & Safin, D. A. (2017b). Inorg. Chem. 56, 9698–9709. CrossRef Google Scholar
Mahmoudi, G., Zangrando, E., Bauza, A., Maniukiewicz, W., Carballo, R., Gurbanov, A. V. & Frontera, A. (2017c). CrystEngComm, 19, 3322–3330. CrossRef Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2017a). Coord. Chem. Rev. 345, 54–72. Web of Science CrossRef Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2017b). Dalton Trans. 46, 10121–10138. Web of Science CrossRef Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Sabbatini, A., Drew, M. G. B., Martins, L. M. D. R. S., Pettinari, C. & Pombeiro, A. J. L. (2014). Inorg. Chem. 53, 9946–9958. Web of Science CrossRef Google Scholar
Mahmudov, K. T. & Pombeiro, A. J. L. (2016). Chem. Eur. J. 22, 16356–16398. Web of Science CrossRef 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, S., Ács, M., Bálint, J. & Fogassy, E. (1994). Acta Cryst. B50, 762–771. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Marthi, K., Larsen, M., Balint, M., Acs, J. & Fogassy, E. (1995). Acta Chem. Scand. 49, 20–27. CrossRef Google Scholar
Mitoraj, M. P., Mahmoudi, G., Afkhami, F. A., Castineiras, A., Garcia-Santos, I., Gurbanov, A. V., Zubkov, F. I., Kukulka, M., Sagan, F., Szczepanik, D. W. & Safin, D. A. (2018). Inorg. Chem. 57, 4395–4408. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shixaliyev, N. Q., Gurbanov, A. V., Maharramov, A. M., Mahmudov, K. T., Kopylovich, M. N., Martins, L. M. D. R. S., Muzalevskiy, V. M., Nenajdenko, V. G. & Pombeiro, A. J. L. (2014). New J. Chem. 38, 4807–4815. CrossRef Google Scholar
Shixaliyev, N. Q., Maharramov, A. M., Gurbanov, A. V., Gurbanova, N. V., Nenajdenko, V. G., Muzalevskiy, V. M. & Mahmudov, K. T. (2013a). J. Mol. Struct. 1041, 213–218. CrossRef Google Scholar
Shixaliyev, N. Q., Maharramov, A. M., Gurbanov, A. V., Nenajdenko, V. G., Muzalevskiy, V. M., Mahmudov, K. T. & &Kopylovich, M. N. (2013b). Catal. Today, 217, 76–79. CrossRef Google Scholar
Spackman, M. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spackman, M. A. & McKinnon, J. J. (2002). CrystEngComm, 4, 378–392. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). CrystalExplorer. University of Western Australia. Google Scholar

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