Green synthesis and crystal structure of 3-(benzo­thia­zol-2-yl)thio­phene

Nguyen Ngoc, L.; Vu Quoc, T.; Duong Quoc, H.; Vu Quoc, M.; Truong Minh, L.; Thang Pham, C.; Van Meervelt, L.

doi:10.1107/S2056989017014530

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1647-1651

https://doi.org/10.1107/S2056989017014530

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Green synthesis and crystal structure of 3-(benzothiazol-2-yl)thiophene

Linh Nguyen Ngoc,^a Trung Vu Quoc,^a Hoan Duong Quoc,^a Manh Vu Quoc,^a,^b Luong Truong Minh,^a Chien Thang Pham ^c and Luc Van Meervelt ^d ^*

^aFaculty of Chemistry, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam, ^bFaculty of Foundation Science, College of Printing Industry, Phuc Dien, Bac Tu Liem, Hanoi, Vietnam, ^cVNU University of Science, Department of Inorganic Chemistry, 19 Le Thanh Tong Street, Hoan Kiem District, Hanoi, Vietnam, and ^dDepartment of Chemistry, KU Leuven, Biomolecular Architecture, Celestijnenlaan 200F, Leuven (Heverlee), B-3001, Belgium
^*Correspondence e-mail: Luc.VanMeervelt@kuleuven.be

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 26 September 2017; accepted 9 October 2017; online 13 October 2017)

The title compound, C₁₁H₇NS₂, was prepared in high yield (87%) using a solvent-free microwave-assisted synthesis. The structure shows whole-molecule disorder with occupancies for two orientations (A and B) of 0.4884 (10) and 0.5116 (10), respectively. The thiophene and benzothiazole rings are almost planar and make dihedral angles of 10.02 (18) and 12.54 (19)° for orientations A and B, respectively. Slipped π–π stacking between the aromatic rings, together with C—H⋯π, C—H⋯S and C—H⋯N interactions, result in a herringbone motif in the crystal packing.

Keywords: crystal structure; thiophene; benzothiazole; microwave-assisted synthesis; solvent-free; whole-molecule disorder.

CCDC reference: 1578811

1. Chemical context

Thiophene-containing heterocycles have many applications in pharmacology, such as anti-inflammatory and analgesic agents (Issa et al., 2009 ), electrochromic and electronic devices (Elbing et al., 2008 ), and polyelectrolytes-based water-soluble sensing agents for the detection of DNA, proteins and small bioanalytes (Ho et al., 2008 ; Feng et al., 2008 ). Benzothiazole-based compounds have attracted much attention in recent times due to their wide-ranging biological activities, such as anticancer, antifungal and antibacterial activities (Aiello et al., 2008 ; Cho et al., 2008 ). In addition, some other 2-aminobenzothiazole derivatives showed antibacterial, anti-inflammatory and analgesic properties (Bhoi et al., 2014 ). A novel poly 3-(benzothiazol-2-yl)thiophene-based conductive polymer has been synthesized by chemical and electrochemical polymerization (Radhakrishnan et al., 2006 ; Radhakrishnan & Somanathan, 2006 ). These polymers were studied for their photoabsorption and photoluminescence characteristics and were investigated in polymeric light-emitting diodes. Some synthetic methods developed for preparing 3-(benzothiazol-2-yl)thiophene are available using a mixture of thiophene-3-carbaldehyde and o-aminothiophenol refluxed in ethanol (Esashika et al., 2009 ) or a mixture of 3-bromothiophene, magnesium turnings and 2-chlorobenzothiazole (Radhakrishnan et al., 2003 ). 2-Substituted benzothiazoles have been synthesized through condensation of bis(2-aminophenyl) disulfides with arylaldehydes catalyzed by NaSH under microwave irradiation (Liu et al., 2017 ). X-ray single-crystal structure determinations of two (1,3-benzothiazol-2-yl)thiophene derivatives synthesized from phenyl isothiocyanate (Fun et al., 2012 ) and benzothiazole (Cheng et al., 2016 ) have been reported, as well as of 4-(1,3-benzothiazol-2-yl)thiophene-2-sulfonamide complexed with cyclin-dependent kinase 5 (Malmström et al., 2012 ). However, 3-(benzothiazol-2-yl)thiophene itself has not been studied by crystallographic methods. In this study, we present a solvent-free microwave-assisted synthesis of 3-(benzothiazol-2-yl)thiophene, starting from thiophene-3-carbaldehyde and o-aminothiophenol, together with its crystal structure determination. The reaction was performed in a short time, without solvent and catalyst, leading to a simple purification protocol and a high yield (87%).

2. Structural commentary

The title compound crystallizes in the monoclinic space group P2₁/c with four molecules in the unit cell. The structure exhibits whole-molecule disorder by a rotation of approximately 180° around an axis running close to the S and N atoms of the benzothiazole ring, resulting in two orientations (A and B) of about the same shape (Fig. 1). In addition, orientations A and B both have similar occupancies of 0.4884 (10) and 0.5116 (10), respectively. All the heterocyclic rings are almost planar, with r.m.s. deviations of 0.017 (thiophene ring S1–C5), 0.004 (thiophene ring S15–C19), 0.010 (benzothiazole ring C6–N14) and 0.021 Å (benzothiazole ring C20–N28). For orientation A, the angle between the best planes through the thiophene and benzothiazole rings is 10.02 (18)°. In orientation B, this angle is 12.54 (19)°. The relatively planar structure of the compound results in intramolecular S⋯H contact distances shorter than the sum of the van der Waals radii of S and H (S7⋯H2 = 2.849 Å and S21⋯H16 = 2.824 Å).

Figure 1
View of the asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small circles of arbitrary radii. Orientation A of the disordered compound (occupancy factor 0.488) is shown in orange.

3. Supramolecular features

The crystal packing of the title compound shows a herringbone motif (Fig. 2). This motif is built up by slipped π–π stacking between the aromatic rings and C—H⋯π interactions. The shortest centroid–centroid distances (Cg⋯Cg) observed in the π–π stacking for orientation B are shown in Fig. 3 and are listed in Table 1 for both orientations. The stacking molecules interact further with neighbouring molecules through C—H⋯π interactions (Fig. 3 and Table 2). In addition, infinite chains running in the [201] direction are formed through C—H⋯N and C—H⋯S interactions (Fig. 4 and Table 2). The crystal packing contains no voids. Whole-molecule disorder is usually caused by a packing which is determined by van der Waals interactions only or by a lack of directional interactions in the packing. However, the crystal packing of the title compound shows several directional interactions, and hence the whole-molecule disorder is the consequence of the very similar interations with neighbouring molecules for the two orientations.

Table 1
Selected π–π interactions

Cg1 is the centroid of the S15/C16–C19 plane, Cg2 that of the C20/S21/C22/C27/N28 plane, Cg3 that of the C22–C27 plane, Cg4 that of the S1/C2–C5 plane, Cg5 that of the C6/S7/C8/C13/N14 plane and Cg6 that of the C8–C13 plane.

CgI	CgJ	Cg–Cg (Å)	α (°)	CgI_Perp (Å)	CgJ_Perp (Å)
Cg1	Cg2ⁱ	3.888 (3)	12.0 (2)	3.761 (2)	−3.7335 (17)
Cg1	Cg3ⁱ	3.962 (3)	13.0 (2)	3.774 (2)	−3.614 (2)
Cg2	Cg1ⁱⁱ	3.888 (3)	12.0 (2)	−3.7335 (17)	3.761 (2)
Cg2	Cg6ⁱⁱ	3.973 (3)	9.4 (2)	−3.6796 (17)	3.708 (2)
Cg3	Cg1ⁱⁱ	3.962 (3)	13.0 (2)	−3.614 (2)	3.774 (2)
Cg3	Cg6ⁱⁱ	3.799 (3)	10.4 (2)	−3.631 (2)	3.720 (2)
Cg4	Cg5ⁱⁱ	3.859 (3)	9.6 (2)	−3.5981 (19)	3.7215 (17)
Cg4	Cg6ⁱⁱ	3.882 (3)	10.4 (2)	−3.5850 (19)	3.674 (2)
Cg5	Cg4ⁱ	3.859 (3)	9.6 (2)	3.7215 (17)	−3.5981 (19)
Cg6	Cg2ⁱ	3.972 (3)	9.4 (2)	3.708 (2)	−3.6796 (17)
Cg6	Cg3ⁱ	3.798 (3)	10.4 (2)	3.719 (2)	−3.631 (2)
Cg6	Cg4ⁱ	3.882 (3)	10.4 (2)	3.673 (2)	−3.5851 (19)
Notes: CgI(J) = plane number I(J); Cg–Cg = distance between ring centroids; CgI_Perp = perpendicular distance of CgI on ring J; CgJ_Perp = perpendicular distance of CgJ on ring I. Symmetry codes: (i) x + 1, y, z; (ii) x − 1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S15/C16–C19 plane, Cg3 that of the C22–C27 plane, Cg4 that of the S1/C2–C5 plane and Cg6 that of the C8–C13 plane.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯N14ⁱ	0.95	2.54	3.355 (6)	144
C26—H26⋯S15ⁱⁱ	0.95	2.87	3.522 (5)	126
C5—H5⋯Cg1ⁱⁱⁱ	0.95	2.86	3.496 (5)	125
C5—H5⋯Cg6ⁱⁱⁱ	0.95	2.93	3.532 (5)	123
C11—H11⋯Cg3^iv	0.95	2.90	3.670 (6)	139
C11—H11⋯Cg4^iv	0.95	2.90	3.705 (6)	143
C19—H19⋯Cg3^iv	0.95	2.74	3.418 (6)	129
C19—H19⋯Cg4^iv	0.95	2.73	3.447 (6)	133
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Crystal packing of the title compound shown in projection down the c axis. Orientation A of the disordered compound (occupancy factor 0.488) is shown in orange.

Figure 3
Slipped π–π stacking between the aromatic rings and C—H⋯π interactions for orientation B. [Symmetry codes: (i) −x + 2, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (ii) x − 1, y, z; (iii) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (iv) x + 1, y, z.]

Figure 4
Infinite chain formation through C—H⋯N (blue dashed lines) and C—H⋯S (yellow dashed lines) interactions in the crystal packing of the title compound. Orientation A of the disordered compound (occupancy factor 0.488) is shown in orange. [Symmetry codes: (i) x − 1, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ; (iii) x + 1, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (iv) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .]

Additional insight into the intermolecular interactions was obtained from an analysis of the Hirshfield surface and two-dimensional fingerprint plots using CrystalExplorer (McKinnon et al., 2007 ; Spackman & Jayatilaka, 2009 ). Fig. 5 illustrates the Hirshfeld surfaces mapped over d_norm for both orientations. The bright-red spots near atoms H9 and N14 for orientation A and near atoms H26 and S15 for orientation B are indicative for the hydrogen bonds given in Table 2. For orientation A, the red spots near atoms S1 and C12 refer to short C⋯S/S⋯C contacts and in the case of S1 also S⋯S contacts. The red spots for orientation B near atoms N28 and H16 characterize short N⋯H/H⋯N contacts, and near atoms H19 and C24 indicate short H⋯C/C⋯H contacts. The relative distributions from the different interatomic contacts to the Hirshfeld surfaces are summarized in Table 3. The largest contributions are contacts in which H atoms are involved. The largest differences between both orientations are observed for H⋯S/S⋯H (9.5%), H⋯H (5.7%), S⋯S (3.3%) and C⋯S/S⋯C (3.1%) contacts, and are caused by the presence of the C26—H26⋯S15ⁱⁱ hydrogen bond in orientation B.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surfaces

Contact	Orientation A	Orientation B
H⋯H	35.8	30.1
S⋯H/H⋯S	15.9	25.4
C⋯H/H⋯C	20.2	21.8
N⋯H/H⋯N	6.4	7.7
C⋯C	8.0	8.9
C⋯S/S⋯C	6.1	3.0
S⋯S	4.2	0.9
S⋯N/N⋯S	2.3	1.1
C⋯N/N⋯C	1.0	1.1

Figure 5
Two views of the Hirshfeld surfaces mapped over d_norm for (a) orientation A in the range −0.151 to 1.099 a.u. and (b) orientation B in the range −0.134 to 0.936 a.u.

4. Database survey

A search of the Cambridge Structral Database (CSD, Version 3.38, last update May 2017; Groom et al., 2016 ) for 3-(benzothiazol-2-yl)thiophene derivatives gives two hits: 2-anilino-4-(1,3-benzothiazol-2-yl)-5-(4-chlorobenzoyl)thiophene-3-carbonitrile (refcode LEGHOW; Fun et al., 2012) and 3-(1,3-benzothiazol-2-yl)-N-(quinolin-8-yl)thiophene-2-carboxamide (refcode UVUGOJ; Cheng et al., 2016). The substitution of the thiophene ring in these two compounds has an influence on the angle between the best planes through the thiophene and benzothiazole rings. In the monosubstituted derivative UVUGOJ, an intramolecular N—H⋯S hydrogen bond lowers the angle to 5.95°. For the trisubstituted derivative LEGHOW, the angle increases to 46.77°.

5. Synthesis and crystallization

The reaction scheme to synthesize the title compound is given in Fig. 6. The reaction mechanism is similar to that described by Mukhopadhyay & Datta (2007 ) for the synthesis of 2-arylbenzothiazoles.

Figure 6
Reaction scheme for the title compound.

A reaction mixture of thiophene-3-carbaldehyde (2 mmol) and o-aminothiophenol (2 mmol) was heated for 4 min in a domestic microwave (Sanyo EM-S1065, 800 W) at medium power level (400 W). The progress of the reaction was monitored with thin-layer chromatography (TLC) every minute. The mixture was cooled to room temperature and then dissolved in an n-hexane–ethyl acetate mixture (5:1 v/v) to obtain a solid product, which was further crystallized in the same solvent to give 0.38 g (yield 87%) of the title product as pale-yellow crystals (m.p. 386 K). IR (Nicolet Impact 410 FT–IR, KBr, cm⁻¹): 3067 (ν_CH), 1581 (ν_C=C), 1634 (ν_C=N). ¹H NMR [Bruker XL-500, 500 MHz, d₆-DMSO, δ (ppm), J (Hz)]: 8.36 (dd, 1H, ⁴J = 1.0, ⁵J = 2.5, H²), 7.72 (dd, 1H, ²J = 1.0, ⁵J = 5.0, H⁴), 7.77 (dd, 1H, ²J = 2.5, ⁴J = 5.0, H⁵), 8.02 (dd, 1H, ¹¹J = 1.0, ¹⁰J = 8.0, H⁹), 7.52 (td, 1H, ¹²J = 1.0, ¹¹J = 7.5, ⁹J = 8.0, H¹⁰), 7.44 (td, 1H, ⁹J = 1.0, ¹⁰J = 7.5, ¹²J = 8.0, H¹¹), 8.11 (dd, 1H, ¹⁰J = 1.0, ¹¹J = 8.0, H¹²). ¹³C NMR [Bruker XL-500, 125 MHz, d₆-DMSO, δ (ppm)]: 127.54 (C²), 135.17 (C³),126.17 (C⁴), 128.38 (C⁵), 162.17 (C⁶), 134.17 (C⁷), 153.30 (C⁸), 122.57 (C⁹), 126.53 (C¹⁰), 125.30 (C¹¹), 122.22 (C¹²). Calculation for C₁₁H₇NS₂: M = 217 a.u.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The molecule is disordered over two positions (A and B) by a rotation of approximately 180°. The final occupancy factors are 0.4884 (10) for molecule A and 0.5116 (10) for molecule B. Enhanced rigid-body restraints (RIGU) were applied for all atoms. The H atoms were placed in idealized positions and refined in riding mode, with U_iso(H) values assigned as 1.2U_eq of the parent atoms, with a C—H distance of 0.95 Å. In the final cycles of refinement, 17 outliers were omitted.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₁H₇NS₂
M_r	217.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.1368 (4), 13.9799 (9), 11.4609 (7)
β (°)	100.193 (2)
V (Å³)	967.73 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.50
Crystal size (mm)	0.44 × 0.36 × 0.31

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.703, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	19256, 2385, 2255
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.172, 1.22
No. of reflections	2385
No. of parameters	254
No. of restraints	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.52
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), SHELXT2016 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1578811

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017014530/tx2001sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017014530/tx2001Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3-(Benzothiazol-2-yl)thiophene top

Crystal data top

C₁₁H₇NS₂	F(000) = 448
M_r = 217.30	D_x = 1.491 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1368 (4) Å	Cell parameters from 9904 reflections
b = 13.9799 (9) Å	θ = 2.9–32.6°
c = 11.4609 (7) Å	µ = 0.50 mm⁻¹
β = 100.193 (2)°	T = 100 K
V = 967.73 (11) Å³	Block, colorless
Z = 4	0.44 × 0.36 × 0.31 mm

Data collection top

Bruker APEXII CCD diffractometer	2255 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.034
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 28.3°, θ_min = 2.9°
T_min = 0.703, T_max = 0.747	h = −8→8
19256 measured reflections	k = −18→18
2385 independent reflections	l = −15→15

Refinement top

Refinement on F²	228 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.076	H-atom parameters constrained
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.0293P)² + 2.8579P] where P = (F_o² + 2F_c²)/3
S = 1.22	(Δ/σ)_max = 0.001
2385 reflections	Δρ_max = 0.61 e Å⁻³
254 parameters	Δρ_min = −0.51 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)
S1	0.1359 (2)	0.50570 (11)	0.64696 (12)	0.0370 (3)	0.4884 (10)
C2	0.3260 (9)	0.5734 (4)	0.5993 (4)	0.0304 (8)	0.4884 (10)
H2	0.332074	0.581845	0.517697	0.036*	0.4884 (10)
C3	0.4732 (7)	0.6159 (3)	0.6887 (4)	0.0208 (6)	0.4884 (10)
C4	0.4069 (8)	0.5922 (3)	0.8006 (4)	0.0242 (7)	0.4884 (10)
H4	0.478997	0.617848	0.874094	0.029*	0.4884 (10)
C5	0.2230 (7)	0.5268 (3)	0.7915 (4)	0.0218 (7)	0.4884 (10)
H5	0.162696	0.500659	0.855346	0.026*	0.4884 (10)
C6	0.6552 (7)	0.6774 (3)	0.6747 (4)	0.0202 (6)	0.4884 (10)
S7	0.68433 (19)	0.71644 (9)	0.53194 (10)	0.0230 (2)	0.4884 (10)
C8	0.9176 (7)	0.7805 (3)	0.5945 (3)	0.0188 (6)	0.4884 (10)
C9	1.0540 (8)	0.8389 (4)	0.5407 (4)	0.0256 (7)	0.4884 (10)
H9	1.026389	0.849650	0.457569	0.031*	0.4884 (10)
C10	1.2293 (8)	0.8799 (4)	0.6130 (4)	0.0294 (8)	0.4884 (10)
H10	1.325861	0.919477	0.577890	0.035*	0.4884 (10)
C11	1.2752 (8)	0.8670 (4)	0.7362 (4)	0.0267 (8)	0.4884 (10)
H11	1.398885	0.897336	0.783337	0.032*	0.4884 (10)
C12	1.1363 (8)	0.8092 (4)	0.7873 (4)	0.0246 (7)	0.4884 (10)
H12	1.163974	0.799310	0.870616	0.029*	0.4884 (10)
C13	0.9581 (7)	0.7659 (3)	0.7183 (4)	0.0196 (6)	0.4884 (10)
N14	0.8042 (6)	0.7076 (3)	0.7618 (3)	0.0213 (6)	0.4884 (10)
S15	1.2597 (2)	0.90620 (10)	0.59226 (10)	0.0325 (3)	0.5116 (10)
C16	1.0318 (8)	0.8344 (4)	0.5615 (4)	0.0260 (8)	0.5116 (10)
H16	0.946788	0.825702	0.484562	0.031*	0.5116 (10)
C17	0.9864 (6)	0.7905 (3)	0.6624 (3)	0.0204 (6)	0.5116 (10)
C18	1.1510 (8)	0.8185 (3)	0.7658 (4)	0.0247 (7)	0.5116 (10)
H18	1.149066	0.795829	0.843803	0.030*	0.5116 (10)
C19	1.3063 (8)	0.8798 (4)	0.7391 (4)	0.0255 (8)	0.5116 (10)
H19	1.425444	0.904712	0.795189	0.031*	0.5116 (10)
C20	0.8024 (7)	0.7272 (3)	0.6680 (4)	0.0216 (6)	0.5116 (10)
S21	0.6485 (2)	0.68370 (9)	0.53382 (10)	0.0282 (3)	0.5116 (10)
C22	0.4817 (7)	0.6220 (3)	0.6160 (4)	0.0255 (6)	0.5116 (10)
C23	0.3070 (8)	0.5607 (4)	0.5775 (5)	0.0319 (8)	0.5116 (10)
H23	0.260774	0.544164	0.496484	0.038*	0.5116 (10)
C24	0.2039 (10)	0.5250 (4)	0.6684 (5)	0.0466 (10)	0.5116 (10)
H24	0.078484	0.485473	0.643384	0.056*	0.5116 (10)
C25	0.2579 (7)	0.5390 (3)	0.7860 (5)	0.0269 (7)	0.5116 (10)
H25	0.175882	0.512781	0.841294	0.032*	0.5116 (10)
C26	0.4498 (7)	0.5970 (4)	0.8198 (4)	0.0276 (7)	0.5116 (10)
H26	0.506396	0.606303	0.901659	0.033*	0.5116 (10)
C27	0.5547 (7)	0.6395 (3)	0.7374 (4)	0.0227 (6)	0.5116 (10)
N28	0.7402 (6)	0.6993 (3)	0.7626 (3)	0.0235 (6)	0.5116 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0362 (6)	0.0388 (7)	0.0338 (6)	−0.0082 (5)	0.0007 (5)	0.0022 (5)
C2	0.0364 (15)	0.0304 (19)	0.0229 (11)	−0.0075 (11)	0.0016 (10)	−0.0026 (12)
C3	0.0204 (10)	0.0211 (14)	0.0209 (10)	0.0033 (8)	0.0036 (8)	−0.0010 (10)
C4	0.0273 (13)	0.0233 (16)	0.0227 (10)	0.0023 (10)	0.0062 (9)	−0.0004 (11)
C5	0.0224 (13)	0.0164 (15)	0.0276 (11)	0.0063 (10)	0.0069 (11)	−0.0006 (12)
C6	0.0221 (10)	0.0205 (14)	0.0180 (10)	0.0019 (8)	0.0038 (8)	−0.0019 (10)
S7	0.0251 (5)	0.0246 (5)	0.0180 (4)	−0.0042 (4)	0.0004 (4)	0.0005 (4)
C8	0.0206 (11)	0.0185 (14)	0.0172 (9)	0.0014 (8)	0.0033 (8)	−0.0023 (9)
C9	0.0310 (13)	0.0225 (16)	0.0257 (12)	−0.0041 (10)	0.0115 (9)	−0.0031 (11)
C10	0.0341 (15)	0.0267 (19)	0.0296 (10)	−0.0065 (12)	0.0116 (10)	−0.0033 (12)
C11	0.0245 (14)	0.0281 (18)	0.0286 (10)	−0.0022 (11)	0.0076 (10)	−0.0038 (12)
C12	0.0242 (12)	0.0293 (16)	0.0205 (12)	−0.0030 (9)	0.0048 (9)	−0.0046 (11)
C13	0.0221 (10)	0.0188 (14)	0.0178 (9)	0.0022 (8)	0.0029 (8)	−0.0004 (9)
N14	0.0224 (10)	0.0225 (14)	0.0185 (10)	0.0005 (9)	0.0020 (8)	0.0000 (10)
S15	0.0324 (5)	0.0418 (6)	0.0241 (4)	−0.0105 (5)	0.0072 (4)	−0.0022 (5)
C16	0.0259 (14)	0.0317 (17)	0.0198 (10)	−0.0032 (11)	0.0026 (10)	−0.0032 (11)
C17	0.0209 (10)	0.0203 (13)	0.0200 (10)	0.0019 (8)	0.0037 (8)	−0.0057 (9)
C18	0.0268 (12)	0.0271 (16)	0.0198 (11)	−0.0038 (10)	0.0030 (9)	−0.0034 (11)
C19	0.0267 (13)	0.0279 (16)	0.0215 (11)	−0.0044 (10)	0.0033 (11)	−0.0019 (12)
C20	0.0200 (10)	0.0206 (13)	0.0233 (10)	0.0012 (8)	0.0009 (8)	−0.0030 (9)
S21	0.0306 (5)	0.0311 (6)	0.0203 (4)	−0.0078 (4)	−0.0028 (4)	0.0016 (4)
C22	0.0258 (12)	0.0208 (14)	0.0279 (10)	−0.0029 (9)	−0.0006 (9)	−0.0009 (10)
C23	0.0302 (14)	0.0231 (16)	0.0374 (13)	−0.0065 (10)	−0.0075 (10)	0.0021 (12)
C24	0.0482 (19)	0.044 (2)	0.0448 (11)	−0.0254 (15)	0.0000 (10)	−0.0028 (12)
C25	0.0213 (13)	0.0174 (16)	0.0412 (11)	0.0018 (10)	0.0029 (11)	0.0000 (13)
C26	0.0242 (12)	0.0260 (16)	0.0327 (12)	−0.0040 (10)	0.0054 (9)	−0.0013 (11)
C27	0.0204 (11)	0.0207 (14)	0.0261 (9)	0.0013 (8)	0.0017 (8)	−0.0018 (9)
N28	0.0234 (11)	0.0225 (13)	0.0242 (9)	−0.0012 (9)	0.0032 (8)	−0.0032 (9)

Geometric parameters (Å, º) top

S1—C2	1.667 (6)	S15—C16	1.707 (5)
C2—H2	0.9500	C16—H16	0.9500
C2—C3	1.375 (6)	C16—C17	1.380 (6)
C3—C4	1.449 (6)	C17—C18	1.468 (6)
C4—H4	0.9500	C18—H18	0.9500
S1—C5	1.674 (5)	S15—C19	1.697 (5)
C4—C5	1.442 (7)	C18—C19	1.357 (7)
C5—H5	0.9500	C19—H19	0.9500
C3—C6	1.442 (6)	C17—C20	1.444 (6)
C6—S7	1.763 (4)	C20—S21	1.764 (4)
S7—C8	1.733 (4)	S21—C22	1.738 (5)
C8—C9	1.389 (6)	C22—C23	1.383 (6)
C9—H9	0.9500	C23—H23	0.9500
C9—C10	1.363 (7)	C23—C24	1.403 (8)
C10—H10	0.9500	C24—H24	0.9500
C10—C11	1.402 (7)	C24—C25	1.344 (8)
C11—H11	0.9500	C25—H25	0.9500
C11—C12	1.378 (7)	C25—C26	1.426 (6)
C12—H12	0.9500	C26—H26	0.9500
C12—C13	1.372 (6)	C26—C27	1.369 (7)
C8—C13	1.411 (5)	C22—C27	1.406 (6)
C6—N14	1.299 (5)	C20—N28	1.273 (6)
C13—N14	1.404 (6)	C27—N28	1.401 (5)

C3—C2—S1	114.0 (4)	C18—C19—S15	111.1 (3)
C4—C5—S1	107.0 (3)	C17—C16—S15	111.6 (3)
C3—C2—H2	123.0	C19—S15—C16	93.7 (2)
S1—C2—H2	123.0	C17—C16—H16	124.2
N14—C6—C3	124.2 (4)	S15—C16—H16	124.2
C5—C4—C3	114.8 (4)	N28—C20—C17	125.4 (4)
C2—C3—C4	108.1 (4)	C19—C18—C17	113.4 (4)
C6—C3—C4	125.4 (4)	C20—C17—C18	124.0 (4)
C5—C4—H4	122.6	C16—C17—C18	110.2 (4)
C3—C4—H4	122.6	C19—C18—H18	123.3
C2—S1—C5	96.0 (2)	C17—C18—H18	123.3
C4—C5—H5	126.5	S15—C19—H19	124.5
S1—C5—H5	126.5	C18—C19—H19	124.5
C2—C3—C6	126.4 (4)	C16—C17—C20	125.8 (4)
C8—S7—C6	89.31 (19)	C22—S21—C20	88.5 (2)
C3—C6—S7	119.8 (3)	C17—C20—S21	118.4 (3)
N14—C6—S7	116.1 (3)	N28—C20—S21	116.2 (3)
C9—C8—S7	129.7 (3)	C23—C22—S21	129.2 (4)
C13—C8—S7	109.1 (3)	C27—C22—S21	109.6 (3)
C10—C9—C8	116.8 (4)	C26—C27—C22	120.0 (4)
N14—C13—C8	115.5 (4)	N28—C27—C22	114.4 (4)
C12—C13—C8	119.7 (4)	C25—C24—C23	129.0 (5)
C8—C9—H9	121.6	C24—C23—H23	122.9
C10—C9—H9	121.6	C22—C23—H23	122.9
C12—C11—C10	118.3 (4)	C22—C23—C24	114.1 (5)
C11—C10—H10	118.2	C23—C24—H24	115.5
C9—C10—H10	118.2	C25—C24—H24	115.5
C9—C10—C11	123.6 (5)	C27—C26—C25	121.7 (4)
C13—C12—C11	120.3 (4)	C26—C25—H25	123.2
C12—C11—H11	120.8	C24—C25—H25	123.2
C10—C11—H11	120.8	C24—C25—C26	113.6 (5)
C11—C12—H12	119.9	C25—C26—H26	119.1
C13—C12—H12	119.9	C27—C26—H26	119.1
C9—C8—C13	121.2 (4)	C20—N28—C27	111.3 (4)
C6—N14—C13	110.0 (4)	C23—C22—C27	121.1 (4)
C12—C13—N14	124.7 (4)	C26—C27—N28	125.6 (4)

C5—S1—C2—C3	1.2 (4)	C19—S15—C16—C17	0.8 (4)
S1—C2—C3—C6	179.5 (4)	S15—C16—C17—C20	178.4 (3)
S1—C2—C3—C4	−3.4 (5)	S15—C16—C17—C18	−0.7 (5)
C2—C3—C4—C5	4.7 (6)	C16—C17—C18—C19	0.1 (6)
C6—C3—C4—C5	−178.3 (4)	C20—C17—C18—C19	−178.9 (4)
C3—C4—C5—S1	−3.8 (5)	C17—C18—C19—S15	0.5 (5)
C2—S1—C5—C4	1.5 (4)	C16—S15—C19—C18	−0.7 (4)
C2—C3—C6—N14	−172.3 (5)	C16—C17—C20—N28	−167.9 (5)
C4—C3—C6—N14	11.2 (7)	C18—C17—C20—N28	11.0 (7)
C2—C3—C6—S7	8.0 (6)	C16—C17—C20—S21	12.2 (6)
C4—C3—C6—S7	−168.5 (4)	C18—C17—C20—S21	−168.9 (3)
N14—C6—S7—C8	−0.5 (4)	N28—C20—S21—C22	0.4 (4)
C3—C6—S7—C8	179.2 (4)	C17—C20—S21—C22	−179.7 (3)
C6—S7—C8—C9	−178.7 (4)	C20—S21—C22—C23	−177.2 (5)
C6—S7—C8—C13	1.2 (3)	C20—S21—C22—C27	0.3 (3)
C13—C8—C9—C10	0.8 (7)	C27—C22—C23—C24	4.4 (7)
S7—C8—C9—C10	−179.3 (4)	S21—C22—C23—C24	−178.3 (4)
C8—C9—C10—C11	−0.8 (8)	C22—C23—C24—C25	−3.2 (9)
C9—C10—C11—C12	0.4 (8)	C23—C24—C25—C26	−1.3 (9)
C10—C11—C12—C13	0.0 (8)	C24—C25—C26—C27	4.9 (7)
C11—C12—C13—N14	−178.5 (4)	C25—C26—C27—N28	178.3 (4)
C11—C12—C13—C8	0.1 (7)	C25—C26—C27—C22	−3.8 (7)
C9—C8—C13—C12	−0.5 (7)	C23—C22—C27—C26	−1.2 (7)
S7—C8—C13—C12	179.6 (4)	S21—C22—C27—C26	−179.0 (4)
C9—C8—C13—N14	178.2 (4)	C23—C22—C27—N28	176.9 (4)
S7—C8—C13—N14	−1.7 (5)	S21—C22—C27—N28	−0.9 (5)
C3—C6—N14—C13	179.9 (4)	C17—C20—N28—C27	179.1 (4)
S7—C6—N14—C13	−0.3 (5)	S21—C20—N28—C27	−1.0 (5)
C12—C13—N14—C6	180.0 (4)	C26—C27—N28—C20	179.2 (4)
C8—C13—N14—C6	1.3 (5)	C22—C27—N28—C20	1.2 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S15/C16–C19 plane, Cg3 that of the C22–C27 plane, Cg4 that of the S1/C2–C5 plane and Cg6 that of the C8–C13 plane.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N14ⁱ	0.95	2.54	3.355 (6)	144
C26—H26···S15ⁱⁱ	0.95	2.87	3.522 (5)	126
C5—H5···Cg1ⁱⁱⁱ	0.95	2.86	3.496 (5)	125
C5—H5···Cg6ⁱⁱⁱ	0.95	2.93	3.532 (5)	123
C11—H11···Cg3^iv	0.95	2.90	3.670 (6)	139
C11—H11···Cg4^iv	0.95	2.90	3.705 (6)	143
C19—H19···Cg3^iv	0.95	2.74	3.418 (6)	129
C19—H19···Cg4^iv	0.95	2.73	3.447 (6)	133

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x−1, −y+3/2, z+1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+2, y+1/2, −z+3/2.

Selected π–π interactions top

CgI	CgJ	Cg–Cg (Å)	Alpha (°)	CgI_Perp (Å)	CgJ_Perp (Å)
Cg1	Cg2ⁱ	3.888 (3)	12.0 (2)	3.761 (2)	-3.7335 (17)
Cg1	Cg3ⁱ	3.962 (3)	13.0 (2)	3.774 (2)	-3.614 (2)
Cg2	Cg1ⁱⁱ	3.888 (3)	12.0 (2)	-3.7335 (17)	3.761 (2)
Cg2	Cg6ⁱⁱ	3.973 (3)	9.4 (2)	-3.6796 (17)	3.708 (2)
Cg3	Cg1ⁱⁱ	3.962 (3)	13.0 (2)	-3.614 (2)	3.774 (2)
Cg3	Cg6ⁱⁱ	3.799 (3)	10.4 (2)	-3.631 (2)	3.720 (2)
Cg4	Cg5ⁱⁱ	3.859 (3)	9.6 (2)	-3.5981 (19)	3.7215 (17)
Cg4	Cg6ⁱⁱ	3.882 (3)	10.4 (2)	-3.5850 (19)	3.674 (2)
Cg5	Cg4ⁱ	3.859 (3)	9.6 (2)	3.7215 (17)	-3.5981 (19)
Cg6	Cg2ⁱ	3.972 (3)	9.4 (2)	3.708 (2)	-3.6796 (17)
Cg6	Cg3ⁱ	3.798 (3)	10.4 (2)	3.719 (2)	-3.631 (2)
Cg6	Cg4ⁱ	3.882 (3)	10.4 (2)	3.673 (2)	-3.5851 (19)

Notes: CgI(J) = plane number I(J); Cg–Cg = distance between ring centroids; CgI_Perp = perpendicular distance of CgI on ring J; CgJ_Perp = perpendicular distance of CgJ on ring I. Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Percentage contributions of interatomic contacts to the Hirshfeld surfaces top

Contact	Orientation A	Orientation B
H···H	35.8	30.1
S···H/H···S	15.9	25.4
C···H/H···C	20.2	21.8
N···H/H···N	6.4	7.7
C···C	8.0	8.9
C···S/S···C	6.1	3.0
S···S	4.2	0.9
S···N/N···S	2.3	1.1
C···N/N···C	1.0	1.1

Funding information

Funding for this research was provided by: VLIR–UOS (award No. ZEIN2014Z182 to LVM).

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