Synthesis, crystal structure and Hirshfeld surface analysis of 4-{(1E)-1-[(car­bamo­thioyl­amino)­imino]­eth­yl}phenyl propano­ate

Madhan, S.; NizamMohideen, M.; Viswanathan, V.; Karthik Ananth, M.; Narasimhan, S.

doi:10.1107/S2056989024003177

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 80| Part 5| May 2024| Pages 489-494

https://doi.org/10.1107/S2056989024003177

Open

access

Synthesis, crystal structure and Hirshfeld surface analysis of 4-{(1E)-1-[(carbamothioylamino)imino]ethyl}phenyl propanoate

Sundarasamy Madhan,^a MohamedHanifa NizamMohideen,^a ^* Vijayan Viswanathan,^b Mani Karthik Ananth ^c and Srinivasan Narasimhan ^d

^aDepartment of Physics, The New College, Chennai 600 014, University of Madras, Tamil Nadu, India, ^bDepartment of Biophysics, All India Institute of Medical Science, New Delhi 110029, India, ^cDepartment of Food Quality & Safety, Institute for Postharvest and Food Sciences, Volcani Center, ARO, Rishon LeZion 7528809, Israel, and ^dDepartment of Chemistry, Asthagiri Herbal Research Foundation, Perungudi Industrial Estate, Chennai 600 096, Tamilnadu, India
^*Correspondence e-mail: mnizam.new@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 March 2024; accepted 12 April 2024; online 18 April 2024)

The title compound, C₁₂H₁₅N₃O₂S, adopts an E configuration with respect to the C=N bond. The propionate group adopts an antiperiplanar (ap) conformation. There are short intramolecular N—H⋯N and C—H⋯O contacts, forming S(5) and S(6) ring motifs, respectively. In the crystal, molecules are connected into ribbons extending parallel to [010] by pairs of N—H⋯S interactions, forming rings with R₂²(8) graph-set motifs, and by pairs of C—H⋯S interactions, where rings with the graph-set motif R₂¹(7) are observed. The O atom of the carbonyl group is disordered over two positions, with a refined occupancy ratio of 0.27 (2):0.73 (2). The studied crystal consisted of two domains.

Keywords: crystal structure; thiosemicarbazone; propionate; hydrogen bonding; Hirshfeld surface analysis; two-dimensional fingerprint.

CCDC reference: 1909895

1. Chemical context

Thiosemicarbazone derivatives have found applications in drug development for the treatment of central nervous system disorders and bacterial infection, as well as analgesic and anti-allergic agents. They are inhibitors of DNA replication and are effective against proteases. This inhibitory activity explains the level of attention given to them in the fight against microbial and parasitic diseases (Mani et al., 2015 ). Moreover, thiosemicarbazones have many biological activities, such as antiparasital (Du et al., 2002 ), antibacterial, antitumour (Papageorgiou et al., 1997 ), anti-African trypanosome (Fatondji et al., 2013 ), antimicrobial, sodium channel blocker, antimalarial, antitubercular (Khanye et al., 2011 ), antiviral (Venkatesh et al., 2016 ), antifungal and locomotor activity (Singh et al., 2011 ), and they are used as a cure for leprosy, rheumatism and trypanosomiasis (Parul et al., 2012 ). They are also important intermediates in organic synthesis, mainly for obtaining heterocyclic rings, such as thiazolidones, oxadiazoles, pyrazolidones and thiadiazoles (Greenbaum et al., 2004 ). Thiosemicarbazones have also received considerable attention in view of their simplicity of preparation and various complexing abilities that can be used in analytical applications (Garg & Jain, 1988 ; Casas et al., 2000 ). They are well known as N,S-donors, with a wide range of coordination modes (Lobana et al., 2009 ).

In view of such important applications, we herein report the crystal structure determination and Hirshfeld surface analysis of the title thiosemicarbazone derivative, namely, 4-{(1E)-1-[(carbamothioylamino)imino]ethyl}phenyl propanoate, (I).

2. Structural commentary

The molecular structure of compound (I) is shown in Fig. 1. It adopts an E configuration with respect to the C10=N1 bond (Fig. 1), showing a C10—N1—N2—C12 torsion angle of 175.4 (2)°. The N1—N2—C12—S1 torsion angle of −171.5 (1)° suggests that the thionyl S1 atom is located trans to the azomethine N1 atom. The C10=N1 bond length [1.285 (6) Å] is close to that of a formal C=N double bond [1.284 (3) Å; Seena et al., 2006 ]. Similarly, the C12=S1 bond length [1.679 (4) Å] is close to that of formal C=S bond [1.685 (3) Å; Jacob & Kurup, 2012 ], and the N1—N2 bond length of 1.369 (5) Å is similar to those found in the Cambridge Structural Database (Allen, 2002 ) for thiosemicarbazone systems (371 hits, mean N—N distance is 1.374 Å). All other bond lengths and angles are normal and correspond well to those observed in the crystal structures of related semicarbazone and thiosemicarbazone derivatives (Carballo et al., 2014 ).

Figure 1
The molecular structure of compound (I)

, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Intramolecular contacts are shown as dashed lines.

The propionate group adopts an antiperiplanar (ap) conformation, as can be seen from the C1—C2—C3—O2 torsion angle of −176.3 (2)°. The semicarbazone unit is nearly planar, showing an N3—C12—N2—N1 torsion angle of 7.4 (2)°. The maximum deviation from the mean plane of the non-H atoms of the C10/C11/C12/N1/N2/N3 fragment is −0.037 (5) Å for the N2 atom. The dihedral angle between this mean plane and the plane of the aromatic ring is 25.3 (1)°. Intramolecular N—H⋯N and C—H⋯O contacts, forming S(5) and S(6) ring motifs (Bernstein et al. 1995 ), respectively, lead to the stabilization of the molecular conformation (Fig. 1 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N1	0.80 (3)	2.27 (5)	2.588 (6)	104 (4)
C5—H5⋯O1B	0.93	2.32	2.812 (7)	113
N2—H2⋯S1ⁱ	0.84 (3)	2.69 (3)	3.525 (4)	173 (4)
N3—H3A⋯S1ⁱⁱ	0.85 (3)	2.55 (3)	3.402 (5)	177 (5)
C11—H11B⋯S1ⁱ	0.96	2.77	3.452 (5)	128
Symmetry codes: (i) ; (ii) .

3. Supramolecular features

Several supramolecular hydrogen-bonding interactions are observed in (I). In the crystal, individual molecules are connected by pairs of N—H⋯S interactions, forming ribbons extending parallel to [010], where rings with $[R_{2}^{2}]$ (8) graph-set motifs (Bernstein et al., 1995) are formed (N2—H2⋯S1 and N3—H3A⋯S1), and by pairs of C11—H11B⋯S1 interactions, where rings with the graph-set motif $[R_{2}^{1}]$ (7) are observed (Fig. 2). C—H⋯π and π–π intermolecular interactions are not present in the crystal.

Figure 2
A view along the a axis of the crystal structure of (I)

. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted.

4. Hirshfeld surface analysis

A recent review by Tiekink and collaborators (Tan et al., 2019 ) describes the use and utility of Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) for analysis of intermolecular contacts in crystals. Corresponding calculations were performed with CrystalExplorer (Spackman et al., 2021 ).

The Hirshfeld surface of compound (I) mapped over d_norm is given in Fig. 3, and the intermolecular contacts are illustrated in Fig. 4(a). They are colour mapped with the normalized contact distance, d_norm, from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii). The d_norm surface was mapped over a fixed colour scale of −0.469 (red) to 1.632 (blue) for (I), where the red spots indicate the intermolecular contacts involved in hydrogen-bonding interactions. The electrostatic potential was also mapped on the Hirshfeld surface using a STO-3G basis set and the Hartee–Fock level of theory (Spackman et al., 2008 ; Jayatilaka et al., 2005 ). The presence of interactions is indicated by a red and blue colour on the shape-index surface [Fig. 4(b)]. Areas on the Hirshfeld surface with high curvedness tend to divide the surface into contact patches with each neighbouring molecule. The number of interacting molecules around a central molecule in the crystal correlates with the curvedness of the Hirshfeld surface [Fig. 4(c)]. The nearest-neighbour coordination environment of a molecule is identified from the colour patches on the Hirshfeld surface depending on their closeness to adjacent molecules [Fig. 4(d)].

Figure 3
The Hirshfeld surface of (I)

, mapped over d_norm.

Figure 4
The Hirshfeld surfaces for visualizing the intermolecular contacts of compound (I)

: (a) d_norm with various intermolecular contacts in the crystal, (b) shape index, (c) curvedness and (d) fragment patches.

The fingerprint plots of (I) are given in Fig. 5. They reveal that the principal intermolecular contacts are H⋯H contacts with a 42.0% contribution [Fig. 5(b)], followed by H⋯C/C⋯H contacts with a 16.5% contribution (Fig. 5c), S⋯H/H⋯S with 15.7% [Fig. 5(d)], O⋯·H/H⋯O with 13.1% [Fig. 5(e)] and N⋯H/H⋯N with 7.1% [Fig. 5(f)]. O⋯O contacts with a contribution of 2.0% [Fig. 5(g)], S⋯C/C⋯S with 1.3% [Fig. 5(h)], O⋯C/C⋯O with 1.1% [Fig. 5(i)], C⋯C with 0.7% [Fig. 5(j)], N⋯N with 0.3% [Fig. 5(k)], N⋯C/C⋯N with 0.2% [Fig. 5(l)] and S⋯N/N⋯S with 0.1% [Fig. 5(m)] contribute less to the packing.

Figure 5
(a) The full two-dimensional fingerprint plot for title compound and those delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) S⋯H/H⋯S, (e) O⋯H/H⋯O, (f) N⋯H/H⋯N, (g) O⋯O, (h) S⋯C/C⋯S, (i) O⋯C/C⋯O, (j) C⋯C, (k) N⋯N, (l) N⋯C/C⋯N and (m) S⋯N/N⋯S contacts.

5. Database survey

Given the interest in semithiocarbazones owing to their biological potential, it is not surprising that a search of the Cambridge Structural Database (CSD, Version 5.37, last update May 2016; Groom et al., 2016 ) revealed almost 100 hits for the CC(H)=NN(H)C(=S)N(H₂) fragment. The only restriction in the search was that the heaviest atom was sulfur. In the absence of this restriction, there were nearly 400 hits. All bond lengths and angles are normal and correspond well to those observed in the crystal structures of related semicarbazone and thiosemicarbazone derivatives (Naik & Palenik, 1974 ; Wang et al., 2004 ; Pelosi et al., 2005 ; Yathirajan et al., 2006 ; Sarojini et al., 2007 ; Reddy et al., 2014 ; Carballo et al., 2014)

6. Synthesis and crystallization

To 4-hydroxyacetophenone (0.5 mol) were added 200 ml of chloroform under continuous stirring and cooling to 288–293 K. Propanoyl chloride (0.5 mol) was added dropwise to the reaction mixture and stirring continued for another 15 min, when 0.5 mol of potassium carbonate were added slowly. The reaction was continued for another 4 h and was monitored using thin-layer chromatography (TLC). The reaction mass was then washed twice with water (2 × 250 ml). The chloroform layer was separated and washed with 10 wt% NaOH solution (2 × 250 ml). The aqueous phase was separated, dried with anhydrous sodium sulfate, followed by concentration under reduced pressure using a rotary vacuum system, and cooled before hexane was added.

Thiosemicarbazide (0.91 g, 0.01 mole) was added to 50 ml of an ethanolic solution of 4-acetylphenyl propionate (0.01 mol) with continuous stirring for 4–5 h. The resulting mixture was refluxed at 333 K and the purity of the products, as well as the composition of the reaction mixture, was monitored by TLC using ethyl acetate–hexane (3:7 v:v). The reaction mixture was cooled to room temperature and the separated product was filtered, dried and finally recrystallized from chloroform solution, yielding colourless crystals of (I).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.96 Å) and included in the refinement in the riding-model approximation, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms. The N-bound H atoms were located in a difference Fourier map and freely refined. The O1 atom of the carbonyl group was found to be disordered over two positions, with a refined occupancy ratio of 0.73 (2):0.27 (2). The C=O bond length and ADPs were subjected to restraints to yield sensible geometrical parameters. The crystal under investigation consists of two domains. The crystal structure was refined using HKLF5-type data with all reflections of component 1 (including the overlapping ones) resulting in a BASF value of 0.3587 (2).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₅N₃O₂S
M_r	265.33
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	5.7700 (1), 8.3069 (2), 14.6243 (5)
α, β, γ (°)	82.891 (2), 87.004 (4), 74.172 (2)
V (Å³)	669.07 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.29 × 0.24 × 0.20

Data collection
Diffractometer	Bruker D8 VENTURE diffractometer with PHOTON II detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.723, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	8530, 8530, 6376
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.219, 1.09
No. of reflections	8530
No. of parameters	188
No. of restraints	197
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.26
Computer programs: APEX3 (Bruker, 2016 ), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ), WinGX (Farrugia, 2012), publCIF (Westrip, 2010 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 1909895

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989024003177/wm5713sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024003177/wm5713Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024003177/wm5713Isup3.cml

checkCIF report

Computing details top

4-[(1E)-1-[(Carbamothioylamino)imino]ethyl]phenyl propanoate top

Crystal data top

C₁₂H₁₅N₃O₂S	Z = 2
M_r = 265.33	F(000) = 280
Triclinic, P1	D_x = 1.317 Mg m⁻³
a = 5.7700 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3069 (2) Å	Cell parameters from 8530 reflections
c = 14.6243 (5) Å	θ = 1.4–25.0°
α = 82.891 (2)°	µ = 0.24 mm⁻¹
β = 87.004 (4)°	T = 296 K
γ = 74.172 (2)°	Block, colourless
V = 669.07 (3) Å³	0.29 × 0.24 × 0.20 mm

Data collection top

Bruker D8 VENTURE diffractometer with PHOTON II detector	6376 reflections with I > 2σ(I)
ω and φ scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −6→6
T_min = 0.723, T_max = 0.863	k = −9→9
8530 measured reflections	l = −17→17
8530 independent reflections

Refinement top

Refinement on F²	197 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.065	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.219	w = 1/[σ²(F_o²) + (0.1179P)² + 0.1922P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
8530 reflections	Δρ_max = 0.26 e Å⁻³
188 parameters	Δρ_min = −0.26 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.

Refinement. Refined as a 2-component twin

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	1.0534 (11)	0.1766 (9)	0.6695 (4)	0.0748 (18)
H1A	1.177682	0.206605	0.699122	0.112*
H1B	1.105508	0.059493	0.660560	0.112*
H1C	0.909702	0.196951	0.707362	0.112*
C2	1.0027 (10)	0.2796 (8)	0.5790 (3)	0.0627 (16)
H2A	0.959090	0.397789	0.588404	0.075*
H2B	1.148613	0.257722	0.541123	0.075*
C3	0.8076 (11)	0.2464 (8)	0.5289 (4)	0.0605 (15)
C4	0.6029 (8)	0.3302 (7)	0.3831 (3)	0.0460 (12)
C5	0.4929 (9)	0.2042 (7)	0.3839 (3)	0.0553 (14)
H5	0.527970	0.112943	0.429410	0.066*
C6	0.3285 (9)	0.2129 (7)	0.3165 (3)	0.0518 (13)
H6	0.257115	0.125208	0.316087	0.062*
C7	0.2684 (8)	0.3510 (6)	0.2492 (3)	0.0392 (11)
C8	0.3902 (8)	0.4745 (7)	0.2493 (3)	0.0443 (12)
H8	0.359427	0.565770	0.203699	0.053*
C9	0.5552 (8)	0.4633 (7)	0.3159 (3)	0.0463 (12)
H9	0.634613	0.546995	0.315112	0.056*
C10	0.0799 (8)	0.3681 (6)	0.1809 (3)	0.0402 (11)
C11	0.0131 (9)	0.2144 (7)	0.1596 (3)	0.0538 (14)
H11A	0.138562	0.115539	0.179483	0.081*
H11B	−0.007165	0.220584	0.094384	0.081*
H11C	−0.134948	0.208693	0.191289	0.081*
C12	−0.3239 (8)	0.7118 (6)	0.0597 (3)	0.0414 (11)
N1	−0.0217 (6)	0.5204 (5)	0.1479 (2)	0.0407 (10)
N2	−0.2082 (7)	0.5502 (5)	0.0885 (3)	0.0420 (10)
N3	−0.2309 (9)	0.8273 (6)	0.0830 (4)	0.0623 (13)
O2	0.7779 (6)	0.3338 (5)	0.4461 (2)	0.0654 (12)
S1	−0.5771 (2)	0.75787 (17)	−0.00106 (11)	0.0586 (5)
O1A	0.829 (7)	0.0938 (10)	0.527 (2)	0.114 (13)	0.27 (2)
O1B	0.6526 (17)	0.1802 (15)	0.5647 (4)	0.084 (4)	0.73 (2)
H2	−0.271 (7)	0.483 (5)	0.067 (3)	0.035 (13)*
H3A	−0.280 (9)	0.930 (5)	0.061 (3)	0.071 (18)*
H3B	−0.105 (6)	0.803 (6)	0.109 (3)	0.051 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.085 (4)	0.079 (5)	0.060 (3)	−0.012 (4)	−0.028 (3)	−0.013 (3)
C2	0.058 (3)	0.080 (5)	0.052 (3)	−0.020 (3)	−0.016 (3)	−0.001 (3)
C3	0.071 (4)	0.059 (4)	0.053 (3)	−0.020 (3)	−0.021 (3)	0.003 (3)
C4	0.039 (2)	0.059 (3)	0.040 (3)	−0.015 (2)	−0.007 (2)	0.001 (3)
C5	0.058 (3)	0.048 (3)	0.054 (3)	−0.010 (3)	−0.019 (3)	0.012 (3)
C6	0.056 (3)	0.043 (3)	0.055 (3)	−0.015 (3)	−0.021 (2)	0.010 (3)
C7	0.035 (2)	0.037 (3)	0.042 (2)	−0.004 (2)	−0.0033 (19)	−0.002 (2)
C8	0.040 (2)	0.046 (3)	0.043 (3)	−0.008 (2)	−0.004 (2)	0.004 (2)
C9	0.044 (3)	0.047 (3)	0.050 (3)	−0.017 (2)	−0.002 (2)	0.001 (3)
C10	0.038 (2)	0.041 (3)	0.038 (2)	−0.006 (2)	−0.002 (2)	−0.002 (2)
C11	0.062 (3)	0.042 (3)	0.056 (3)	−0.010 (3)	−0.021 (3)	−0.001 (3)
C12	0.040 (2)	0.039 (3)	0.045 (3)	−0.013 (2)	−0.008 (2)	0.004 (2)
N1	0.039 (2)	0.043 (3)	0.038 (2)	−0.0112 (18)	−0.0095 (16)	0.0066 (19)
N2	0.043 (2)	0.033 (2)	0.049 (2)	−0.0095 (19)	−0.0146 (18)	0.005 (2)
N3	0.067 (3)	0.039 (3)	0.081 (3)	−0.017 (3)	−0.044 (3)	0.012 (3)
O2	0.064 (2)	0.084 (3)	0.055 (2)	−0.037 (2)	−0.0220 (18)	0.015 (2)
S1	0.0527 (8)	0.0359 (8)	0.0871 (10)	−0.0128 (6)	−0.0365 (7)	0.0107 (7)
O1A	0.15 (3)	0.056 (13)	0.14 (2)	−0.027 (13)	−0.08 (2)	0.014 (12)
O1B	0.087 (6)	0.125 (9)	0.058 (4)	−0.065 (6)	−0.017 (4)	0.011 (4)

Geometric parameters (Å, º) top

C1—C2	1.480 (7)	C7—C8	1.393 (6)
C1—H1A	0.9600	C7—C10	1.482 (6)
C1—H1B	0.9600	C8—C9	1.375 (6)
C1—H1C	0.9600	C8—H8	0.9300
C2—C3	1.479 (7)	C9—H9	0.9300
C2—H2A	0.9700	C10—N1	1.285 (6)
C2—H2B	0.9700	C10—C11	1.502 (7)
C3—O1B	1.234 (8)	C11—H11A	0.9600
C3—O1A	1.242 (2)	C11—H11B	0.9600
C3—O2	1.327 (6)	C11—H11C	0.9600
C4—C9	1.363 (7)	C12—N3	1.305 (6)
C4—C5	1.362 (7)	C12—N2	1.351 (6)
C4—O2	1.410 (5)	C12—S1	1.679 (4)
C5—C6	1.386 (6)	N1—N2	1.369 (5)
C5—H5	0.9300	N2—H2	0.84 (3)
C6—C7	1.394 (7)	N3—H3A	0.85 (3)
C6—H6	0.9300	N3—H3B	0.80 (3)

C2—C1—H1A	109.5	C6—C7—C10	121.7 (4)
C2—C1—H1B	109.5	C9—C8—C7	120.9 (5)
H1A—C1—H1B	109.5	C9—C8—H8	119.6
C2—C1—H1C	109.5	C7—C8—H8	119.6
H1A—C1—H1C	109.5	C4—C9—C8	120.4 (5)
H1B—C1—H1C	109.5	C4—C9—H9	119.8
C3—C2—C1	113.6 (5)	C8—C9—H9	119.8
C3—C2—H2A	108.8	N1—C10—C7	114.6 (4)
C1—C2—H2A	108.8	N1—C10—C11	125.6 (4)
C3—C2—H2B	108.8	C7—C10—C11	119.7 (4)
C1—C2—H2B	108.8	C10—C11—H11A	109.5
H2A—C2—H2B	107.7	C10—C11—H11B	109.5
O1B—C3—O2	121.3 (5)	H11A—C11—H11B	109.5
O1A—C3—O2	113.3 (14)	C10—C11—H11C	109.5
O1B—C3—C2	124.9 (5)	H11A—C11—H11C	109.5
O1A—C3—C2	113.1 (12)	H11B—C11—H11C	109.5
O2—C3—C2	111.6 (5)	N3—C12—N2	116.7 (4)
C9—C4—C5	120.6 (4)	N3—C12—S1	122.8 (4)
C9—C4—O2	114.3 (4)	N2—C12—S1	120.6 (4)
C5—C4—O2	125.1 (5)	C10—N1—N2	119.1 (4)
C4—C5—C6	119.7 (5)	C12—N2—N1	118.2 (4)
C4—C5—H5	120.2	C12—N2—H2	111 (3)
C6—C5—H5	120.2	N1—N2—H2	131 (3)
C5—C6—C7	121.0 (5)	C12—N3—H3A	122 (4)
C5—C6—H6	119.5	C12—N3—H3B	121 (4)
C7—C6—H6	119.5	H3A—N3—H3B	115 (4)
C8—C7—C6	117.4 (4)	C3—O2—C4	124.5 (4)
C8—C7—C10	120.9 (4)

C1—C2—C3—O1B	20.2 (11)	C6—C7—C10—N1	154.4 (4)
C1—C2—C3—O1A	−47 (2)	C8—C7—C10—C11	158.8 (4)
C1—C2—C3—O2	−176.3 (5)	C6—C7—C10—C11	−22.2 (6)
C9—C4—C5—C6	−0.9 (8)	C7—C10—N1—N2	−176.1 (3)
O2—C4—C5—C6	−178.1 (5)	C11—C10—N1—N2	0.3 (7)
C4—C5—C6—C7	−1.8 (8)	N3—C12—N2—N1	7.4 (7)
C5—C6—C7—C8	3.6 (7)	S1—C12—N2—N1	−171.5 (3)
C5—C6—C7—C10	−175.4 (4)	C10—N1—N2—C12	175.4 (4)
C6—C7—C8—C9	−2.8 (7)	O1B—C3—O2—C4	−14.7 (11)
C10—C7—C8—C9	176.3 (4)	O1A—C3—O2—C4	52 (2)
C5—C4—C9—C8	1.8 (8)	C2—C3—O2—C4	−178.9 (5)
O2—C4—C9—C8	179.2 (4)	C9—C4—O2—C3	161.2 (5)
C7—C8—C9—C4	0.2 (7)	C5—C4—O2—C3	−21.5 (8)
C8—C7—C10—N1	−24.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N1	0.80 (3)	2.27 (5)	2.588 (6)	104 (4)
C5—H5···O1B	0.93	2.32	2.812 (7)	113
N2—H2···S1ⁱ	0.84 (3)	2.69 (3)	3.525 (4)	173 (4)
N3—H3A···S1ⁱⁱ	0.85 (3)	2.55 (3)	3.402 (5)	177 (5)
C11—H11B···S1ⁱ	0.96	2.77	3.452 (5)	128

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

Acknowledgements

The authors thank the SAIF, IIT, Madras, India, for the data collection.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2016). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carballo, R., Pino-Cuevas, A. & Vázquez-López, E. M. (2014). Acta Cryst. E70, o970. CSD CrossRef IUCr Journals Google Scholar
Casas, J. S., García-Tasende, M. S. & Sordo, J. (2000). Coord. Chem. Rev. 209, 197–261. Web of Science CrossRef CAS Google Scholar
Du, X., Guo, C., Hansell, E., Doyle, P. S., Caffrey, C. R., Holler, T. P., McKerrow, J. H. & Cohen, F. E. (2002). J. Med. Chem. 45, 2695–2707. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fatondji, H. R., Kpoviessi, S., Gbaguidi, F., Bero, J., Hannaert, V., Quetin-Leclercq, J., Poupaert, J., Moudachirou, M. & Accrombessi, G. C. (2013). Med. Chem. Res. 22, 2151–2162. Web of Science CrossRef CAS Google Scholar
Garg, B. S. & Jain, V. K. (1988). Microchem. J. 38, 144–169. CrossRef CAS Web of Science Google Scholar
Greenbaum, D. C., Mackey, Z., Hansell, E., Doyle, P. S., Gut, J., Caffrey, C. R., Lehrman, J., Rosenthal, P. J., McKerrow, J. H. & Chibale, K. (2004). J. Med. Chem. 47, 3212–3219. CrossRef PubMed CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Jacob, J. M. & Kurup, M. R. P. (2012). Acta Cryst. E68, o836–o837. CSD CrossRef CAS IUCr Journals Google Scholar
Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO – A System for Computational Chemistry. Available at: http://hirshfeldsurface.net/. Google Scholar
Khanye, S. D., Wan, B., Franzblau, S. G., Gut, J., Rosenthal, P. J., Smith, G. S. & Chibale, K. (2011). J. Organomet. Chem. 696, 3392–3396. Web of Science CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Lobana, T. S., Sharma, R., Bawa, G. & Khanna, S. (2009). Coord. Chem. Rev. 253, 977–1055. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mani, K. A., Viswanathan, V., Narasimhan, S. & Velmurugan, D. (2015). Acta Cryst. E71, o43–o44. CSD CrossRef IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Naik, D. V. & Palenik, G. J. (1974). Acta Cryst. B30, 2396–2401. CSD CrossRef IUCr Journals Web of Science Google Scholar
Papageorgiou, A., Iakovidou, Z., Mourelatos, D., Mioglou, E., Boutis, L., Kotsis, A., Kovala-Demertzi, D., Domopoulou, A., West, D. X. & Dermetzis, M. A. (1997). Anticancer Res. 17, 247–251. CAS PubMed Google Scholar
Parul, N., Subhangkar, N. & Arun, M. (2012). Inter. Res. J. Phar. 3, 350–363. Google Scholar
Pelosi, G., Pelizzi, C., Belicchi Ferrari, M., Rodríguez-Argüelles, M. C., Vieito, C. & Sanmartín, J. (2005). Acta Cryst. C61, o589–o592. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Reddy, M. S., Sarala, Y., Jagadeesh, M., Das, S. K. & Ammireddy, V. R. (2014). Acta Cryst. E70, o846. CSD CrossRef IUCr Journals Google Scholar
Sarojini, B. K., Narayana, B., Bindya, S., Yathirajan, H. S. & Bolte, M. (2007). Acta Cryst. E63, o2946. Web of Science CSD CrossRef IUCr Journals Google Scholar
Seena, E. B., Manoj, E. & Kurup, M. R. P. (2006). Acta Cryst. C62, o486–o488. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Singh, R., Mishra, P. S. & Mishra, R. (2011). Inter. J. Pharm Tech. Res. 3, 1625–1629. Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Tan, S. L., Jotani, M. M. & Tiekink, E. R. T. (2019). Acta Cryst. E75, 308–318. Web of Science CrossRef IUCr Journals Google Scholar
Venkatesh, K., Rayam, P., Sekhar, K. P. C. & Mukkanti, K. (2016). Int. J. Appl. Biol. Pharm. Tech. 7, 258–266. CAS Google Scholar
Wang, J.-L., Jia, Y.-J. & Yu, M. (2004). Acta Cryst. E60, o662–o663. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yathirajan, H. S., Bindya, S., Narayana, B., Sarojini, B. K. & Bolte, M. (2006). Acta Cryst. E62, o5925–o5926. Web of Science CSD CrossRef IUCr Journals Google Scholar

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