Crystal structure, Hirshfeld surface, DFT and mol­ecular docking studies of 2-{4-[(E)-(4-acetylphen­yl)diazen­yl]phen­yl}-1-(5-bromo­thio­phen-2-yl)ethanone; a compound with bromine⋯oxygen-type contacts

Santhosh Kumar, S.; Srinivasa, H.T.; Harish Kumar, M.; Devarajegowda, H.C.; Palakshamurthy, B.S.

doi:10.1107/S2056989024010776

research communications

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ISSN: 2056-9890

Volume 80| Part 12| December 2024| Pages 1308-1312

https://doi.org/10.1107/S2056989024010776

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Crystal structure, Hirshfeld surface, DFT and molecular docking studies of 2-{4-[(E)-(4-acetylphenyl)diazenyl]phenyl}-1-(5-bromothiophen-2-yl)ethanone; a compound with bromine⋯oxygen-type contacts

S. Santhosh Kumar,^a H.T Srinivasa,^b M. Harish Kumar,^c H. C. Devarajegowda ^c and B. S. Palakshamurthy ^a ^*

^aDepartment of PG Studies and Research in Physics, Albert Einstein Block, UCS, Tumkur University, Tumkur, Karnataka-572103, India, ^bRaman Research Institute, C. V. Raman Avenue, Sadashivanagar, Bangalore, Karnataka, India, and ^cDepartment of Physics, Yuvaraja's College, University of Mysore, Mysore 570005, Karnataka, India
^*Correspondence e-mail: palaksha.bspm@gmail.com

Edited by F. F. Ferreira, Universidade Federal do ABC, Brazil (Received 25 September 2024; accepted 7 November 2024; online 22 November 2024)

The title compound, C₁₉H₁₃BrN₂O₃S, a non-liquid crystal molecule, crystallizes in the orthorhombic system, space group Pna2₁. The torsion angles associated with ester and azo groups are −177.0 (4)°, -anti-periplanar, and 179.0 (4)°, +anti-periplanar, respectively. The packing is consolidated by a weak C—Br⋯O=C contact, forming infinite chains running along the [001] direction. A Hirshfeld surface analysis revealed that the major contributions to the crystal surface are from H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, Br⋯H/H⋯Br and S⋯H/H⋯S interactions. The computed three-dimensional energy interactions using the basis set B3LYP\631-G(d,p) show that E_dis (217.6 kJ mol⁻¹) is the major component in the structure. The DFT calculations performed at the B3LYP/6–311+ G(d,p) level indicate that the energy gap between HOMO and LUMO is 3.6725 (2) eV. The molecular electrostatic potential (MEP) map generated supports the existence of the Br⋯O type contact, formed between the electrophilic site of the bromine atom and the nucleophilic site of the ketonic oxygen atom. The molecular docking between the ligand and the Mycobacterium Tuberculosis (PDB ID:1HZP) receptor shows a good binding affinity value of −8.5 kcal mol⁻¹.

Keywords: crystal structure; azobenzene; molecular docking; C—Br⋯O=C contact; DFT and Hirshfeld surface.

CCDC reference: 2401081

1. Chemical context

Azobenzenes are a class of molecules having high structural similarity with stilbenes, which exhibit antibacterial and antifungal activity (Piotto et al., 2013 ). They are capable of regulating the structure and function of various biological molecules, including proteins, nucleic acids, lipids and peptides (Mulatihan et al., 2020 ). Azobenzene derivatives exhibit biological activities such as antioxidant, antiviral and antimicrobial properties (Ventura & Wiedman, 2021 ; Kaur & Narasimhan, 2018 ; Peddie & Abell, 2019 ). Azobenzene-based polymeric nanocarriers are biocompatible materials and they can accelerate drug-release systems in biological tissues (Londoño-Berrío et al., 2022 ). Interestingly thiophene-based derivatives exhibit significant anti-leishmanial activity (Félix et al., 2016 ) and antimalarial activity (Akolkar et al., 2022 ). The thiophene derivatives with antitubulin properties are potential materials for the treatment of cancer and Alzheimer's and Parkinson's diseases (Romagnoli et al., 2007 ). The thiophene-thiazole derivatives are a class of materials having antitubulin properties and they can also be used as anti-breast cancer agents (Al-Said et al., 2011 ). Azobenzenes, and their derivatives in a trans confirmation, are medically important. They are also useful in industry because of their interesting photoswitch properties and have therefore been widely explored as photoresponsive compounds in materials science (Li et al., 2024 ). Keeping photoswitching properties in mind, we have planed to use the tris(azobenzene) as a core group in the construction of liquid-crystal materials. Hence, we developed the title molecule, (I), to analyse the molecular properties both experimentally and theoretically and present the results herein.

2. Structural commentary

The molecular structure of compound (I) is shown in Fig. 1. In the molecule, the dihedral angles between the five-membered thiophene and the benzene and phenylethanone rings are 1.6 (2) and 54.0 (2)°, respectively, while that between the aromatic rings is 52.5 (2)°. The torsion angles associated with the ester (C—C—O—C) and azo (C—N=N—C) groups in the molecule are -anti-periplanar [−177.0 (4)°] and +anti-periplanar [179.0 (4)°], respectively. Intramolecular C13—H13⋯N1, C10—H10⋯N2, and C16—H16⋯O3 interactions (Table 1) stabilize the molecular structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯N1	0.95	2.47	2.722 (6)	95
C16—H16⋯O3	0.95	2.49	2.788 (6)	98
C10—H10⋯N2	0.95	2.45	2.705 (6)	95

Figure 1
Molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

The crystal packing is consolidated by C1—Br1⋯O3=C18 type interaction with a Br1⋯O3 distance 3.014 (2) Å, forming infinite chains running in the [001] direction as shown in Fig. 2.

Figure 2
Molecular packing of the title compound, Dashed lines indicate C—Br⋯O=C intramolecular contacts.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.42, update of November 2020; Groom et al., 2016 ) for molecules containing the trans(azobenzene) fragment resulted in two matches with CSD refcodes APOPUR, APOQAY and APOQEC (Soegiarto et al., 2010 ). In APOPUR, 4,4′-azobenzenedisulfonate is associated with two azobenzene molecules, one of which is disordered, with the another having a tris conformation. The torsion angles at the azo and azobenzene groups are180.00 and −179.96°. In APOQAY, the 4,4′- dibenzyldisulfonate moiety is associated with two azobenzene fragments in which the torsion angles at the azo groups are 180.0 and178.39° and have a tris conformation. In APOQEC, the 4,4′-stilbenedisulfonate is associated with two azobenzene moieties with torsion angles at the azo group of 180 and −177.93 (2)°. These are comparable with the torsion angle at the azo group of 179.0 (4)° in the tris(azobenzene) fragment of the title molecule. In all these compounds, the torsion angles at the azo group are anti..

5. Hirshfeld surface analysis and interaction energies

A Hirshfeld surface analysis was carried out to quantify the various intermolecular interactions contributed to the crystal using CrystalExplorer17.5 (Turner et al., 2017 ). Fig. 3 illustrates the Hirshfeld surface mapped over d_norm with red spots corresponding to short C—Br⋯O=C contacts. It is an additional confirmation of the presence of Br⋯O type contacts (i.e halogen–oxygen type). In Fig. 4, the sharp spikes in the Br⋯O/O⋯Br fingerprint plot indicate the existence of a weak halogen⋯oxygen interaction in the molecular structure. Although it is a weak interaction, the packing of the title compound is consolidated by Br⋯O interactions and no other interactions are present. The fingerprint plots showing all interactions and those delineated into H⋯H, C⋯H/H⋯C, O⋯H/ H⋯O, Br⋯H/H⋯Br and S⋯H/H⋯S interactions as shown in Fig. 5.

Figure 3
Hirshfeld surface mapped over d_norm with red spots corresponding to short C—Br⋯O=C contacts.

Figure 4
The two-dimensional fingerprint plots (spikes) showing the halogen–oxygen interactions.

Figure 5
The two-dimensional fingerprint plots showing all interactions and those delineated into H⋯H, C⋯H/H⋯C, O⋯H/ H⋯O, Br⋯H/H⋯Br and S⋯H/H⋯S interactions.

Three-dimensional energy interactions were computed for the title compound using the B3LYP\631-G(d,p) basis set, indicating that the E_dis = 217.6 kJ mol⁻¹ is the major component, the others being E_ele = 55.3 kJ mol⁻¹, E_pol =11.6 kJ mol⁻¹, E_rep = 148.6 kJ mol⁻¹ with a total interaction energy E_tot of 164.7 kJ mol⁻¹. The energy frameworks for the interaction energies are shown in Fig. 6.

Figure 6
The energy frameworks for the interaction energies in the title compound (a) Coulombic energy, (b) dispersion energy, (c) total energy and (d) total energy annotated.

6. DFT Studies

The molecular structure of the title compound in the gas phase was optimized using density functional theory with the standard B3LYP method with the basis set 6-311++G(d,p). The input files were prepared from the CIF file using Mercury (Macrae et al., 2020 ) and Gauss View 6.0 (Frisch et al., 2009 ). The electron density distribution in the frontier molecular orbital are shown in Fig. 7. The highest occupied molecular orbital (HOMO) is −6.7179 eV) and the lowest unoccupied molecular orbital (LUMO) is −3.0454 eV) with an energy gap of 3.6725 eV. The electrophilicity index (ω) is 6.489 eV, which indicates the molecule is highly reactive.

Figure 7
The HOMO and LUMO orbitals of the title molecule.

The molecular electrostatic potential (MEP) map predicts the reactive sites for electrophilic and nucleophilic attack present in the molecule. In the crystal, the molecular charge distribution is between −5.108 × 10⁻² and +5.108 × 10⁻² and is governed by the MEP (Fig. 8). The red colour around the oxygen atoms of the ester group and ketone group in the molecule indicates nucleophilic sites and the pale-blue colour around the bromine atom indicate the active electrophilic site. In the crystal, the Br⋯O type contact formed between the electrophilic site of the bromine atom and the nucleophilic site of the ketonic oxygen atom connects the molecule into infinite chains along the c-axis direction.

Figure 8
The molecular electrostatic potential (MEP) surface of the title molecule.

7. Molecular docking

The molecular docking studies using AutoDock tools (Huey et al., 2012 ) were carried out to calculate the degree of binding affinity between the synthesised ligand and the receptor protein of Mycobacterium Tuberculosis bacteria (PDB ID:1HZP). It is found that, among the several interactions with the target protein, four conventional hydrogen-bonding interactions are seen between four moieties, which are formed by the oxygen and nitrogen atoms of the ketonic, ester and azo groups, as shown in Fig. 9. The centroids of the benzene rings (Cg1, C6–C11 and Cg2, C12–C17) attack different amino acid groups (ILE A:156, VAL A:212, ALA A:246 and ARG A:36). PLATON (Spek, 2020 ) indicates very weak π–π stacking between these rings with Cg1⋯Cg2 separations of 5.609 (3) to 5.616 (2) Å; these stacking interactions were able to attack the aforementioned amino acids of the protein. In addition to these, the bromine atom in the molecule has an affinity with another amino acid group (PRO A:210) through nucleophilic attacks. In total, the ligand shows a good binding affinity value of −8.5 kcal mol⁻¹.

Figure 9
Three-dimensional and two-dimensional views of various interactions between the title compound (ligand) and Myobacterium Tuberculosis bacteria (PDB ID:1HZP; receptor protein).

8. Synthesis and crystallization

5-Bromothiophene-2-carboxylic acid (1 eq, 0.207 g), (E)-1-{4-[(4-hydroxyphenyl)diazenyl]phenyl}ethan-1-one (1 eq, 0.240 g), dicyclohexylcarbodiimide (1.2 eq) and a catalytic amount of dimethylaminopyrimidine were stirred in dry dichloromethane at room temperature overnight. Completion of the reaction was verified by thin layer chromatography on silica gel on an aluminium plate with dichloromethane as the mobile phase. After completion of the reaction, the whole reaction mass was subjected to column chromatography with silica gel and a 1:9 ratio of petroleum ether and dichloromethane as eluent. The solvent was evaporated under vacuum, and the crude product was recrystallized from pure chloroform to obtain single crystals suitable for single-crystal X-ray studies. The compound is orange in colour, m.p. 469 K, molecular weight is 429.29. Elemental analysis, calculated: C, 53.16; H, 3.05; Br, 18.61; N, 6.53; O, 11.18; S, 7.47; found: C, 53.19; H, 3.09; N, 6.60; S, 7.52%. ¹H NMR: (500 MHz, CDCl₃) δ/ppm, 8.13–7.97 (m, 6H, Ar-H), 7.76 (d, 1H, J = 6 Hz, Ar-H), 7.43 (m, 2H, Ar-H), 7.18 (m, 1H, Ar-H), 1.57 (s, 3H, COCH₃) ppm. ¹³C NMR (CDCl₃) δ/ppm: 197.5, 159.1, 154.9, 152.8, 138.5, 135.3, 131.4, 122.9, 26.9.

9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All the H-atoms were positioned with idealized geometry and refined using a riding model with C—H = 0.95–0.98 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The crystal studied was refined as an inversion twin.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃BrN₂O₃S
M_r	429.28
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	10.5425 (13), 3.8532 (5), 42.419 (4)
V (Å³)	1723.1 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.53
Crystal size (mm)	0.41 × 0.28 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.431, 0.633
No. of measured, independent and observed [I > 2σ(I)] reflections	36482, 5305, 5216
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.091, 1.23
No. of reflections	5305
No. of parameters	237
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −1.54
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.021 (12)
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ) and Mercury (Macrae et al., 2020).

Supporting information

CCDC reference: 2401081

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024010776/ee2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024010776/ee2010Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024010776/ee2010Isup3.cml

checkCIF report

Computing details top

2-{4-[(E)-(4-Acetylphenyl)diazenyl]phenyl}-1-(5-bromothiophen-2-yl)ethanone top

Crystal data top

C₁₉H₁₃BrN₂O₃S	D_x = 1.655 Mg m⁻³
M_r = 429.28	Melting point: 469 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71074 Å
Hall symbol: P 2c -2n	Cell parameters from 5305 reflections
a = 10.5425 (13) Å	θ = 2.8–30.1°
b = 3.8532 (5) Å	µ = 2.53 mm⁻¹
c = 42.419 (4) Å	T = 120 K
V = 1723.1 (4) Å³	Prism, orange
Z = 4	0.41 × 0.28 × 0.18 mm
F(000) = 864

Data collection top

Bruker SMART APEXII CCD diffractometer	5305 independent reflections
Radiation source: fine-focus sealed tube	5216 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 0.99 pixels mm^-1	θ_max = 30.6°, θ_min = 2.9°
φ and Ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −5→5
T_min = 0.431, T_max = 0.633	l = −60→60
36482 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0229P)² + 3.5453P] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max < 0.001
5305 reflections	Δρ_max = 1.12 e Å⁻³
237 parameters	Δρ_min = −1.54 e Å⁻³
1 restraint	Absolute structure: Refined as an inversion twin
0.132 constraints	Absolute structure parameter: 0.021 (12)
Primary atom site location: structure-invariant direct methods

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.

Refinement. Refined as a 2-component inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.72359 (4)	0.43138 (12)	0.72407 (2)	0.02567 (11)
S1	0.65138 (10)	0.3319 (3)	0.65409 (3)	0.01799 (19)
O2	0.7849 (3)	0.5368 (9)	0.56998 (7)	0.0209 (6)
O1	0.6053 (3)	0.2541 (11)	0.58516 (8)	0.0261 (7)
O3	0.3469 (4)	0.5729 (11)	0.29358 (10)	0.0296 (9)
C2	0.8653 (4)	0.6201 (12)	0.66779 (11)	0.0213 (9)
H2	0.934208	0.714315	0.679421	0.026*
N1	0.6770 (4)	0.4543 (10)	0.44152 (9)	0.0180 (7)
N2	0.5674 (3)	0.5376 (10)	0.43322 (9)	0.0181 (7)
C3	0.8591 (4)	0.6110 (12)	0.63421 (10)	0.0173 (8)
H3	0.924322	0.694646	0.620752	0.021*
C6	0.7507 (4)	0.5120 (11)	0.53813 (10)	0.0167 (7)
C18	0.4512 (4)	0.4762 (13)	0.30191 (11)	0.0213 (8)
C8	0.8114 (4)	0.3473 (12)	0.48602 (10)	0.0177 (8)
H8	0.870799	0.246549	0.471880	0.021*
C17	0.4310 (4)	0.6460 (12)	0.38941 (10)	0.0186 (8)
H17	0.372427	0.744592	0.403888	0.022*
C11	0.6381 (4)	0.6597 (12)	0.52722 (10)	0.0184 (8)
H11	0.580744	0.768563	0.541366	0.022*
C13	0.6316 (4)	0.3619 (12)	0.37891 (10)	0.0177 (8)
H13	0.709212	0.267351	0.386355	0.021*
C14	0.6021 (4)	0.3488 (12)	0.34710 (10)	0.0178 (8)
H14	0.659950	0.245795	0.332706	0.021*
C16	0.4025 (4)	0.6309 (11)	0.35762 (11)	0.0169 (8)
H16	0.323815	0.720403	0.350343	0.020*
C9	0.6980 (4)	0.4834 (11)	0.47477 (10)	0.0161 (7)
C7	0.8372 (4)	0.3598 (12)	0.51804 (10)	0.0181 (8)
H7	0.913759	0.264461	0.526070	0.022*
C1	0.7600 (4)	0.4768 (12)	0.68108 (10)	0.0199 (8)
C4	0.7478 (4)	0.4672 (12)	0.62360 (10)	0.0158 (7)
C12	0.5465 (4)	0.5149 (11)	0.39993 (10)	0.0159 (7)
C10	0.6122 (4)	0.6435 (11)	0.49528 (10)	0.0169 (7)
H10	0.535967	0.741241	0.487273	0.020*
C5	0.7016 (4)	0.4050 (11)	0.59146 (10)	0.0182 (8)
C15	0.4873 (4)	0.4867 (11)	0.33604 (10)	0.0175 (8)
C19	0.5478 (5)	0.3457 (17)	0.27848 (12)	0.0320 (11)
H19A	0.578978	0.117756	0.285185	0.048*
H19B	0.618949	0.509129	0.277391	0.048*
H19C	0.508350	0.325653	0.257643	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0321 (2)	0.02593 (19)	0.01893 (16)	−0.00111 (18)	−0.0019 (2)	0.0010 (2)
S1	0.0169 (4)	0.0172 (4)	0.0199 (4)	−0.0016 (4)	0.0006 (4)	−0.0011 (4)
O2	0.0166 (14)	0.0271 (16)	0.0189 (14)	−0.0018 (13)	0.0006 (11)	−0.0014 (12)
O1	0.0262 (17)	0.0306 (19)	0.0214 (15)	−0.0109 (15)	0.0015 (13)	−0.0022 (15)
O3	0.0244 (17)	0.038 (2)	0.0266 (18)	0.0038 (16)	−0.0022 (15)	−0.0007 (16)
C2	0.0172 (19)	0.022 (2)	0.025 (2)	0.0016 (16)	−0.0047 (15)	−0.0030 (16)
N1	0.0166 (15)	0.0185 (16)	0.0189 (16)	0.0009 (13)	0.0018 (13)	0.0005 (14)
N2	0.0151 (15)	0.0209 (17)	0.0183 (16)	−0.0007 (14)	0.0023 (13)	−0.0016 (13)
C3	0.0128 (17)	0.020 (2)	0.0193 (18)	−0.0001 (15)	−0.0004 (14)	0.0010 (15)
C6	0.0141 (17)	0.0180 (18)	0.0179 (17)	−0.0029 (14)	0.0008 (14)	−0.0004 (15)
C18	0.024 (2)	0.022 (2)	0.0188 (19)	0.0004 (17)	0.0018 (16)	−0.0020 (16)
C8	0.0114 (16)	0.0192 (19)	0.0225 (19)	−0.0002 (15)	0.0046 (14)	−0.0009 (15)
C17	0.0166 (18)	0.0174 (18)	0.0217 (19)	−0.0016 (16)	0.0043 (15)	−0.0015 (15)
C11	0.0156 (18)	0.0177 (18)	0.0218 (18)	0.0006 (15)	0.0028 (14)	−0.0037 (15)
C13	0.0134 (16)	0.0199 (19)	0.0198 (18)	0.0023 (15)	0.0028 (14)	−0.0001 (15)
C14	0.0162 (17)	0.0159 (18)	0.0213 (18)	−0.0012 (15)	0.0042 (15)	−0.0019 (15)
C16	0.0135 (17)	0.0138 (18)	0.0234 (19)	0.0011 (14)	0.0019 (15)	−0.0024 (16)
C9	0.0132 (16)	0.0148 (18)	0.0202 (17)	−0.0013 (14)	0.0021 (13)	0.0006 (14)
C7	0.0127 (17)	0.0193 (18)	0.0222 (19)	0.0027 (15)	0.0018 (15)	−0.0009 (15)
C1	0.023 (2)	0.0185 (19)	0.0181 (18)	0.0058 (16)	−0.0019 (15)	−0.0024 (15)
C4	0.0105 (16)	0.0177 (18)	0.0193 (18)	−0.0005 (14)	0.0010 (13)	−0.0002 (14)
C12	0.0141 (17)	0.0149 (17)	0.0186 (17)	−0.0022 (14)	0.0029 (14)	−0.0008 (14)
C10	0.0142 (17)	0.0151 (17)	0.0214 (19)	−0.0015 (15)	0.0026 (14)	−0.0018 (15)
C5	0.0205 (19)	0.0163 (19)	0.0179 (17)	0.0006 (15)	0.0033 (15)	−0.0023 (15)
C15	0.0183 (18)	0.0163 (18)	0.0179 (18)	−0.0032 (15)	0.0034 (14)	0.0009 (15)
C19	0.033 (3)	0.041 (3)	0.022 (2)	0.009 (2)	0.0062 (19)	−0.005 (2)

Geometric parameters (Å, º) top

Br1—C1	1.872 (4)	C8—C7	1.386 (6)
S1—C1	1.713 (5)	C8—C9	1.391 (6)
S1—C4	1.725 (4)	C8—H8	0.9500
O2—C5	1.364 (5)	C17—C16	1.383 (6)
O2—C6	1.402 (5)	C17—C12	1.392 (6)
O1—C5	1.200 (6)	C17—H17	0.9500
O3—O3	0.000 (15)	C11—C10	1.384 (6)
O3—C18	1.214 (6)	C11—H11	0.9500
C2—C1	1.362 (7)	C13—C14	1.385 (6)
C2—C3	1.427 (6)	C13—C12	1.396 (6)
C2—H2	0.9500	C13—H13	0.9500
N1—N1	0.000 (13)	C14—C15	1.403 (6)
N1—N2	1.250 (5)	C14—H14	0.9500
N1—N2	1.250 (5)	C16—C15	1.394 (6)
N1—C9	1.432 (6)	C16—H16	0.9500
N2—N2	0.000 (13)	C9—C10	1.398 (6)
N2—C12	1.432 (5)	C7—H7	0.9500
C3—C4	1.374 (6)	C4—C5	1.467 (6)
C3—H3	0.9500	C10—H10	0.9500
C6—C7	1.379 (6)	C19—H19A	0.9800
C6—C11	1.395 (6)	C19—H19B	0.9800
C18—C15	1.497 (6)	C19—H19C	0.9800
C18—C19	1.510 (6)

C1—S1—C4	90.5 (2)	C17—C16—H16	119.4
C5—O2—C6	116.9 (3)	C15—C16—H16	119.4
C1—C2—C3	111.5 (4)	C8—C9—C10	120.6 (4)
C1—C2—H2	124.3	C8—C9—N1	116.2 (4)
C3—C2—H2	124.3	C10—C9—N1	123.2 (4)
N2—N1—C9	113.6 (4)	C8—C9—N1	116.2 (4)
N2—N1—C9	113.6 (4)	C10—C9—N1	123.2 (4)
N1—N2—C12	113.9 (3)	C6—C7—C8	119.4 (4)
N1—N2—C12	113.9 (3)	C6—C7—H7	120.3
C4—C3—C2	112.1 (4)	C8—C7—H7	120.3
C4—C3—H3	123.9	C2—C1—S1	113.6 (3)
C2—C3—H3	123.9	C2—C1—Br1	127.5 (3)
C7—C6—C11	122.1 (4)	S1—C1—Br1	118.9 (3)
C7—C6—O2	117.0 (4)	C3—C4—C5	130.8 (4)
C11—C6—O2	120.7 (4)	C3—C4—S1	112.3 (3)
O3—C18—C15	120.2 (4)	C5—C4—S1	116.8 (3)
O3—C18—C15	120.2 (4)	C17—C12—C13	120.7 (4)
O3—C18—C19	121.5 (5)	C17—C12—N2	115.4 (4)
O3—C18—C19	121.5 (5)	C13—C12—N2	123.8 (4)
C15—C18—C19	118.3 (4)	C17—C12—N2	115.4 (4)
C7—C8—C9	119.5 (4)	C13—C12—N2	123.8 (4)
C7—C8—H8	120.3	C11—C10—C9	120.1 (4)
C9—C8—H8	120.3	C11—C10—H10	120.0
C16—C17—C12	119.2 (4)	C9—C10—H10	120.0
C16—C17—H17	120.4	O1—C5—O2	125.2 (4)
C12—C17—H17	120.4	O1—C5—C4	124.5 (4)
C10—C11—C6	118.3 (4)	O2—C5—C4	110.2 (4)
C10—C11—H11	120.8	C16—C15—C14	119.0 (4)
C6—C11—H11	120.8	C16—C15—C18	118.9 (4)
C14—C13—C12	119.6 (4)	C14—C15—C18	122.2 (4)
C14—C13—H13	120.2	C18—C19—H19A	109.5
C12—C13—H13	120.2	C18—C19—H19B	109.5
C13—C14—C15	120.4 (4)	H19A—C19—H19B	109.5
C13—C14—H14	119.8	C18—C19—H19C	109.5
C15—C14—H14	119.8	H19A—C19—H19C	109.5
C17—C16—C15	121.2 (4)	H19B—C19—H19C	109.5

C9—N1—N2—C12	179.0 (4)	C16—C17—C12—N2	−179.3 (4)
C1—C2—C3—C4	1.3 (6)	C14—C13—C12—C17	1.7 (7)
C5—O2—C6—C7	−126.7 (4)	C14—C13—C12—N2	179.2 (4)
C5—O2—C6—C11	58.0 (6)	C14—C13—C12—N2	179.2 (4)
C7—C6—C11—C10	1.6 (7)	N1—N2—C12—C17	−172.4 (4)
O2—C6—C11—C10	176.7 (4)	N1—N2—C12—C17	−172.4 (4)
C12—C13—C14—C15	−0.3 (7)	N1—N2—C12—C13	10.0 (6)
C12—C17—C16—C15	0.1 (7)	N1—N2—C12—C13	10.0 (6)
C7—C8—C9—C10	2.3 (7)	C6—C11—C10—C9	−0.3 (7)
C7—C8—C9—N1	−178.7 (4)	C8—C9—C10—C11	−1.7 (7)
C7—C8—C9—N1	−178.7 (4)	N1—C9—C10—C11	179.5 (4)
N2—N1—C9—C8	171.0 (4)	N1—C9—C10—C11	179.5 (4)
N2—N1—C9—C8	171.0 (4)	C6—O2—C5—O1	4.3 (7)
N2—N1—C9—C10	−10.1 (6)	C6—O2—C5—C4	−177.0 (4)
N2—N1—C9—C10	−10.1 (6)	C3—C4—C5—O1	174.6 (5)
C11—C6—C7—C8	−1.0 (7)	S1—C4—C5—O1	−3.6 (6)
O2—C6—C7—C8	−176.2 (4)	C3—C4—C5—O2	−4.2 (7)
C9—C8—C7—C6	−1.0 (7)	S1—C4—C5—O2	177.7 (3)
C3—C2—C1—S1	−0.5 (5)	C17—C16—C15—C14	1.3 (7)
C3—C2—C1—Br1	−179.5 (3)	C17—C16—C15—C18	179.8 (4)
C4—S1—C1—C2	−0.3 (4)	C13—C14—C15—C16	−1.2 (6)
C4—S1—C1—Br1	178.8 (3)	C13—C14—C15—C18	−179.6 (4)
C2—C3—C4—C5	−179.7 (5)	O3—C18—C15—C16	−4.3 (7)
C2—C3—C4—S1	−1.5 (5)	O3—C18—C15—C16	−4.3 (7)
C1—S1—C4—C3	1.0 (4)	C19—C18—C15—C16	175.2 (4)
C1—S1—C4—C5	179.5 (4)	O3—C18—C15—C14	174.1 (5)
C16—C17—C12—C13	−1.6 (7)	O3—C18—C15—C14	174.1 (5)
C16—C17—C12—N2	−179.3 (4)	C19—C18—C15—C14	−6.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N1	0.95	2.47	2.722 (6)	95
C16—H16···O3	0.95	2.49	2.788 (6)	98
C10—H10···N2	0.95	2.45	2.705 (6)	95

Acknowledgements

The authors thank Kishore and Shivakumar, C., SSCU, IISc, for their help in collecting the SCXRD data and the BSPM lab, Albert Einstein Block, UCS, for the software and other facilities to complete this work.

Funding information

Funding for this research was provided by: Vision Group of Science and Technology (award No. GRD319 to B. S. Palakshamurthy).

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