Crystal structure and Hirshfeld surface analysis of (Z)-4-chloro-N′-(4-oxo­thia­zol­idin-2-yl­idene)benzene­sulfono­hydrazide monohydrate

Pai, N.; Foro, S.; Thimme Gowda, B.

doi:10.1107/S2056989018013658

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ISSN: 2056-9890

Volume 74| Part 11| November 2018| Pages 1569-1573

https://doi.org/10.1107/S2056989018013658

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Crystal structure and Hirshfeld surface analysis of (Z)-4-chloro-N′-(4-oxothiazolidin-2-ylidene)benzenesulfonohydrazide monohydrate

Nikhila Pai,^a Sabine Foro ^b and B. Thimme Gowda ^a,^c ^*

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Str. 2, D-64287, Darmstadt, Germany, and ^cKarnataka State Rural Development and Panchayat Raj University, Gadag 582 101, India
^*Correspondence e-mail: gowdabt@yahoo.com

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 11 September 2018; accepted 25 September 2018; online 12 October 2018)

The asymmetric unit of the title thiazole derivative containing a sulfonylhydrazinic moiety, C₉H₈ClN₃O₃S₂·H₂O, consists of two independent molecules and two water molecules. The central parts of the molecules are twisted as both the molecules are bent at both the S and N atoms. In the crystal, N—H⋯N, N—H⋯O, C—H⋯O and O—H⋯O hydrogen-bonding interactions connect the molecules, forming layers parallel to the ab plane. Two-dimensional fingerprint plots associated with the Hirshfeld surface show that the largest contributions to the crystal packing come from O⋯H/H⋯O (32.9%) and H⋯H (22.6%) interactions.

Keywords: crystal structure; thiazole derivative; hydrogen bonds; Hirshfeld surface analysis.

CCDC reference: 1869597

1. Chemical context

Sulfonamides are of interest as this class of compounds exhibits a wide array of biological activities such as antitumor, antibacterial, diuretic and hypoglycaemic activities (Kamal et al., 2007 ). It has been reported that incorporation of hydrazine moieties increases the carbonic anhydrase inhibition activity (Winum et al., 2005 ). Along with the sulfonamide group, the presence of the 2-hydrazino-thiazole moiety enhances the pharmacological activities. The thiozoyl group is of interest because of its medicinal use in antitumor (Holla et al., 2003 ; Kappe et al., 2004 ), hyposensitive (Dash et al., 1980 ), anti-HIV (Patt et al., 1992 ), antimicrobial and anticancer agents (Frère et al., 2003 ). Sulfonylhydrazines and their derivatives can easily be prepared and are stable. We report herein the synthesis and structure of the title compound, which is a new thiazole compound containing a sulfonylhydrazinic moiety.

2. Structural commentary

The asymmetric unit of the title compound contains two independent molecules and two water molecules (Fig. 1). The C8—O3 and C17—O6 bond lengths of 1.202 (5) Å, 1.218 (6) Å, respectively, are consistent with C=O double-bond character. Similarly, the values of the C7—N2 and C16—N5 bond lengths [1.285 (5) and 1.276 (5) Å, respectively] are close to that of a typical C=N double bond, while the longer C7—N3 and C16—N6 bond lengths of 1.370 (5) and 1.381 (5) Å, respectively, are consistent with the normal C—N single bonds, indicating that the compound exists in the Schiff base form. Further, the N1—N2 and N4—N5 bond lengths of 1.440 (5) and 1.442 (5) Å, respectively, and the S1—N1 and S3—N4 bond lengths of 1.644 (4) and 1.649 (4) Å, respectively, are in agreement with single-bond character.

Figure 1
The molecular structure of the title compound showing displacement ellipsoids at the 50% probability level.

The central parts of both molecules are twisted as they are bent at the S (S1 and S3) and N (N2 and N5) atoms as indicated by the C1—S1—N1—N2 and S1—N1—N2—C7 torsion angles of 57.0 (3) and 111.8 (3)°, respectively, and by the C10—S3—N4—N5 and S3—N4—N5—C16 torsion angles of 57.6 (3) and 109.7 (3)°, respectively. The sulfonylhydrazide bond exists in the synclinal conformation preferred by aromatic sulfonamides (Purandara et al., 2017 ), with C—S—N—N torsion angles of 57.0 (3) and 57.6 (3)° in the two independent molecules. The geometrical parameters for the thiazole and benzene rings are within the expected ranges and comparable with those of other substituted thiazoles or benzenesulfonylhydrazide derivatives (Zaharia et al., 2010 ). The C7—S2—C9 and C16—S4—C18 angles in the two molecules have the same value of 91.4 (2)°, and it is similar to the angles typically observed in thiazole derivatives (Form et al., 1974 ). The thiazole rings are approximately planar (r.m.s. deviations of 0.011 and 0.029 Å for S2/N3/C7–C9 and S4/N6/C16–C18, respectively), and form dihedral angles of 26.18 (15) and 37.19 (12)° with the aromatic ring of the p-chlorophenylsulfonyl groups.

3. Supramolecular features

In the crystal, the two independent molecules are linked into dimers by pairs of N—H⋯N hydrogen bonds, forming rings with an R₂²(8) graph-set motif. These dimers are connected by C—H⋯O hydrogen bonds involving the thiazole C—H and a sulfonyl O atom into chains running parallel to the a axis (Table 1, Fig. 2). The water molecules are involved both in the enforcement of the dimers through N—H⋯O and O—H⋯O hydrogen bonds, forming R₃³(9) rings, and in inter-chain O—H⋯O hydrogen-bonding interactions, forming layers parallel to the ab plane.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O7ⁱ	0.84 (2)	2.07 (2)	2.900 (6)	168 (4)
N3—H3N⋯N5ⁱⁱ	0.85 (2)	2.07 (2)	2.895 (5)	162 (4)
C9—H9B⋯O2ⁱⁱ	0.97	2.42	3.236 (6)	141
N4—H4N⋯O8	0.85 (2)	1.95 (2)	2.788 (6)	168 (4)
N6—H6N⋯N2ⁱⁱⁱ	0.85 (2)	1.97 (2)	2.808 (5)	170 (4)
C15—H15⋯O1^iv	0.93	2.55	3.355 (5)	145
O7—H71⋯O5	0.82 (2)	2.08 (3)	2.868 (5)	162 (6)
O7—H72⋯O6^iv	0.82 (2)	1.99 (2)	2.810 (5)	174 (6)
O8—H81⋯O4ⁱⁱ	0.82 (2)	2.35 (6)	2.987 (6)	136 (7)
O8—H81⋯O7ⁱⁱ	0.82 (2)	2.50 (7)	3.034 (7)	124 (7)
O8—H82⋯O3ⁱⁱⁱ	0.83 (2)	2.37 (3)	3.159 (7)	159 (8)
Symmetry codes: (i) x-1, y+1, z; (ii) x-1, y, z; (iii) x+1, y, z; (iv) x, y-1, z.

Figure 2
The molecular packing of the title compound, with hydrogen bonds (Table 1

) shown as dashed lines.

4. Database survey

Although a search in the Cambridge. Structural Database (CSD, Version 5.39, update of August 2018; Groom et al., 2016 ) revealed several reports of the crystal structure of sulfonamides and thiazole (Gowda et al., 2008 , 2009 ), there are only a few reports on the crystal structures of sulfonylhydrazides functionalized by thiazole groups (Zaharia et al., 2010). Comparison of the structure of the title compound with that of N′-(5-acetyl-4-methyl-4,5-dihydrothiazol-2-yl)benzenesulfonohydrazide (Zaharia et al., 2010) indicates that the electron-withdrawing chloro group does not impart sufficient inductive effect to reduce the electron density on the benzene ring, and that the ability of the aromatic C—H groups to participate in C—H⋯O interactions is very much reduced. Partial double-bond character is observed between the hydrazinyl N atom and the adjacent benzothiazole moiety in 2-[2-(3-nitrobenzenesulfonyl)hydrazinyl]-1,3-benzothiazole (Morscher et al., 2018 ). The orientation of the thiazole ring in the title compound is similar to that of (Z)-methyl 2-[(Z)-4-oxo-2-(2-tosylhydrazono)thiazolidin-5-ylidene]acetate and (Z)-methyl-2-[(Z)-2-(ethylimino)-4-oxo-3-(phenylamino)thiazolidin-5-ylidene]acetate (Hassan et al., 2016 ). The molecule of N′-{3-[3-(trifluoromethyl)phenyl]-1,3-thiazol-2(3H)-ylidene}benzenesulfonohydrazide (Chen et al., 2015 ) is observed to have a Schiff base conformation.

5. Hirshfeld Surface Analysis

In order to explore the role of weak intermolecular interactions in the crystal packing, Hirshfeld surfaces (d_norm) and related fingerprint plots were generated using CrystalExplorer17.5 (McKinnon et al., 2007 ; Spackman et al., 2008 ; Spackman & Jayatilaka, 2009 ; Wolff et al., 2012 ). The three-dimensional molecular Hirshfeld surfaces were generated using a high standard surface resolution over a colour scale of −0.6355 to 1.5137 a.u. for d_norm. To identify the normalized contacts, the d_norm function is used, which is expressed as; d_norm = (d_i − r_i^vdw)/r_i^vdw + (d_e − r_e^vdw)/r_e^vdw (Shit et al., 2016 ), where d_i and d_e are the distances from internal and external atoms to the Hirshfeld surface and r_i^vdw and r_e^vdw are the van der Waals radii of the atoms inside and outside the surface. On the Hirshfeld surfaces mapped over d_norm (Fig. 3), strong N—H⋯N and S—O⋯H interactions are observed as red spots close to atoms N5, N6 and O6. Furthermore, the two-dimensional fingerprint plots indicate that the largest contributions are from O⋯H/H⋯O contacts, which contribute 32.9% to the Hirshfeld surface (Fig. 4a) with d_i + d_e ∼ 1.9 Å. The presence of water molecules in the unit cell provides the largest contribution to the stability of the crystal packing. The next largest contributor is from H⋯H interactions, which contribute 22.6%. A single sharp spike can be seen in the middle region of the plot, at d_i = d_e = 0.9 Å (Fig. 4b). The N⋯H contacts, which refer to N—H⋯N interactions, contribute 5.3% to the surface. Two sharp spikes having d_i + d_e = 1.8 Å (Fig. 4c) are observed. The C⋯H contacts contribute 5.9% to the Hirshfeld surface, featuring a wide region with d_i + d_e = 3.1 Å (Fig. 4d). The different interatomic contacts and percentage contributions to the Hirshfeld surface are Cl⋯H/H⋯Cl (8.3%), S⋯H/H⋯S (6.1%), Cl⋯O/O⋯Cl (3.0%), Cl⋯C/C⋯Cl (2.4%), S⋯O/O⋯S (1.7%), and C⋯O/O⋯C (1.6%) as depicted in the fingerprint plots (Fig. 5a–f).

Figure 3
View of the Hirshfeld surface mapped over d_norm.

Figure 4
The two dimensional fingerprint (FP) plot for the title compound, delineated into (a) O⋯H/H⋯O, (b) H⋯H, (c) N⋯H/H⋯N and (d) C⋯H/H⋯C interactions. d_norm surfaces for each plot indicating the relevant surface patches associated with the specific contacts are shown on the left.

Figure 5
Fingerprint plots of interactions, listing their percentage contributions: (a) Cl⋯H/H⋯Cl, (b) S⋯H/H⋯S, (c) Cl⋯O/O⋯Cl, (d) Cl⋯C/C⋯Cl, (e) S⋯O/O⋯S and (f) C⋯O/O⋯C.

6. Synthesis and crystallization

4-Chloro-N′-(4-oxo-4,5-dihydro-1,3-thiazol-2-yl)benzene-1-sulfonohydrazide was prepared by adding 4-chloro benzenesulfonyl chloride (0.02 mol) under stirring to a solution of thiosemicarbazide (0.02 mol) in 5% aqueous NaOH solution (20 ml). The reaction mixture was stirred at room temperature for 1 h, then diluted twofold with water and neutralized with glacial acetic acid. The solid 2-(4-chlorobenzene-1-sulfonyl)hydrazine-1-carbothioamide (A) obtained was crystallized from acetic acid. Monochloroacetic acid (0.01 mol) and anhydrous sodium acetate (0.04 mol) were added to A (0.01 mol) in glacial acetic acid. The reaction mixture was refluxed for 8–10 h and the completion of the reaction was checked by TLC. The reaction mixture was then poured into cold water. The resulted precipitate of the title compound was separated by vacuum filtration. Prismatic colourless single crystals of the title compound were grown from a mixture of acetonitrile-DMF (5:1 v/v) by slow evaporation of the solvent. The purity of the compound was checked by TLC and characterized by IR spectroscopy. The characteristic IR absorptions observed at 3095.9, 1639.5, 1458.7, 1343.2, 1139.4, and 1215.7 cm⁻¹ correspond to N—H, C=O, C=N, S=O asymmetric and symmetric, and C—S absorptions, respectively. The ¹H and ¹³C spectra of the title compound are as follows: ¹H (400MHz, DMSO-d₆); δ 3.45 (d, 2H, –CH₂), 7.68–7.86 (m, 4H, Ar—H), 10.01 (s, 1H), 11.96 (s, 1H). ¹³C NMR (400 MHz, DMSO-d₆); δ 36.8, 128.4, 129.1, 131.1,132.5, 133.9, 137.2, 165.4, 185.5.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bonded to C were positioned with idealized geometry using a riding model with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene). The H atoms of the NH groups and the H atoms of the water molecules were located in a difference-Fourier map and later refined with the N—H and O—H bond lengths constrained to be 0.86 (2) and 0.82 (2) Å, respectively. All H atoms were refined with isotropic displacement parameters set at 1.2U_eq of the parent atom.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₈ClN₃O₃S₂·H₂O
M_r	323.77
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.6276 (6), 11.090 (1), 17.116 (2)
α, β, γ (°)	96.95 (1), 99.49 (1), 106.08 (1)
V (Å³)	1350.8 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.60
Crystal size (mm)	0.42 × 0.20 × 0.06

Data collection
Diffractometer	Oxford Diffraction Xcalibur Single Crystal X-ray diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England.]$ )
T_min, T_max	0.785, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	8631, 4935, 3375
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.161, 1.05
No. of reflections	4935
No. of parameters	367
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.25
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England.]$ ), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1869597

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018013658/rz5243sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018013658/rz5243Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018013658/rz5243Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(Z)-4-Chloro-N'-(4-oxothiazolidin-2-ylidene)benzenesulfonohydrazide monohydrate top

Crystal data top

C₉H₈ClN₃O₃S₂·H₂O	Z = 4
M_r = 323.77	F(000) = 664
Triclinic, P1	D_x = 1.592 Mg m⁻³
a = 7.6276 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.090 (1) Å	Cell parameters from 2682 reflections
c = 17.116 (2) Å	θ = 2.8–27.8°
α = 96.95 (1)°	µ = 0.60 mm⁻¹
β = 99.49 (1)°	T = 293 K
γ = 106.08 (1)°	Prism, colourless
V = 1350.8 (2) Å³	0.42 × 0.20 × 0.06 mm

Data collection top

Oxford Diffraction Xcalibur Single Crystal X-ray diffractometer with a Sapphire CCD detector	3375 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.026
Rotation method data acquisition using ω scans	θ_max = 25.4°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→5
T_min = 0.785, T_max = 0.965	k = −13→13
8631 measured reflections	l = −20→20
4935 independent reflections

Refinement top

Refinement on F²	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0767P)² + 1.1929P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4935 reflections	Δρ_max = 0.52 e Å⁻³
367 parameters	Δρ_min = −0.25 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
Cl1	0.33684 (17)	0.77231 (13)	0.00096 (7)	0.0689 (4)
S1	0.23228 (14)	1.01774 (10)	0.33163 (6)	0.0479 (3)
S2	−0.21540 (16)	0.96967 (12)	0.42899 (7)	0.0594 (3)
O1	0.3605 (4)	1.1427 (3)	0.35513 (19)	0.0659 (9)
O2	0.2255 (4)	0.9268 (3)	0.38508 (18)	0.0626 (8)
O3	−0.6004 (5)	0.6450 (3)	0.3600 (2)	0.0732 (10)
N1	0.0248 (5)	1.0382 (3)	0.3165 (2)	0.0484 (8)
H1N	0.024 (6)	1.086 (4)	0.282 (2)	0.058*
N2	−0.1246 (4)	0.9225 (3)	0.2827 (2)	0.0471 (8)
N3	−0.3702 (4)	0.7765 (3)	0.3134 (2)	0.0460 (8)
H3N	−0.380 (6)	0.721 (3)	0.2726 (19)	0.055*
C1	0.2676 (5)	0.9482 (4)	0.2392 (2)	0.0421 (9)
C2	0.2102 (6)	0.8168 (4)	0.2167 (3)	0.0515 (10)
H2	0.1557	0.7651	0.2505	0.062*
C3	0.2345 (6)	0.7627 (4)	0.1432 (3)	0.0523 (11)
H3	0.1967	0.6747	0.1273	0.063*
C4	0.3146 (5)	0.8409 (4)	0.0946 (2)	0.0475 (10)
C5	0.3755 (7)	0.9718 (5)	0.1168 (3)	0.0617 (12)
H5	0.4315	1.0231	0.0831	0.074*
C6	0.3514 (7)	1.0250 (4)	0.1899 (3)	0.0577 (12)
H6	0.3920	1.1131	0.2060	0.069*
C7	−0.2275 (5)	0.8889 (4)	0.3335 (2)	0.0419 (9)
C8	−0.4741 (6)	0.7422 (5)	0.3700 (3)	0.0522 (11)
C9	−0.4074 (6)	0.8429 (5)	0.4445 (3)	0.0600 (12)
H9A	−0.3669	0.8068	0.4905	0.072*
H9B	−0.5080	0.8761	0.4549	0.072*
Cl2	0.8418 (2)	0.63805 (14)	0.57661 (8)	0.0805 (4)
S3	0.78365 (15)	0.43436 (10)	0.21411 (7)	0.0511 (3)
S4	0.74715 (17)	0.59857 (12)	0.02143 (7)	0.0603 (3)
O4	0.9602 (4)	0.4892 (3)	0.1948 (2)	0.0670 (9)
O5	0.7003 (5)	0.2980 (3)	0.1978 (2)	0.0691 (9)
O6	0.8569 (5)	0.9655 (4)	0.0519 (2)	0.0762 (10)
N4	0.6297 (5)	0.4853 (3)	0.1590 (2)	0.0501 (9)
H4N	0.541 (5)	0.458 (4)	0.183 (3)	0.060*
N5	0.6762 (5)	0.6224 (3)	0.1738 (2)	0.0468 (8)
N6	0.7780 (5)	0.8026 (3)	0.12079 (19)	0.0473 (8)
H6N	0.804 (6)	0.847 (4)	0.1678 (15)	0.057*
C10	0.8011 (5)	0.4900 (4)	0.3167 (3)	0.0461 (10)
C11	0.9365 (6)	0.6028 (4)	0.3554 (3)	0.0593 (12)
H11	1.0191	0.6482	0.3273	0.071*
C12	0.9484 (6)	0.6473 (4)	0.4349 (3)	0.0605 (12)
H12	1.0383	0.7233	0.4607	0.073*
C13	0.8276 (6)	0.5797 (4)	0.4762 (3)	0.0540 (11)
C14	0.6935 (6)	0.4666 (5)	0.4392 (3)	0.0611 (12)
H14	0.6137	0.4207	0.4682	0.073*
C15	0.6792 (6)	0.4226 (4)	0.3595 (3)	0.0566 (11)
H15	0.5875	0.3474	0.3339	0.068*
C16	0.7281 (5)	0.6717 (4)	0.1146 (2)	0.0438 (9)
C17	0.8171 (6)	0.8523 (5)	0.0550 (3)	0.0575 (12)
C18	0.8040 (7)	0.7499 (5)	−0.0134 (3)	0.0652 (13)
H18A	0.9219	0.7657	−0.0308	0.078*
H18B	0.7080	0.7488	−0.0586	0.078*
O7	0.9751 (5)	0.1699 (4)	0.1821 (3)	0.0766 (10)
H71	0.880 (5)	0.191 (6)	0.182 (4)	0.092*
H72	0.933 (8)	0.112 (4)	0.143 (3)	0.092*
O8	0.3062 (6)	0.4099 (6)	0.2195 (4)	0.1111 (16)
H81	0.195 (4)	0.390 (7)	0.199 (4)	0.133*
H82	0.303 (12)	0.472 (5)	0.250 (4)	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0697 (8)	0.0852 (9)	0.0517 (7)	0.0274 (7)	0.0175 (6)	−0.0042 (6)
S1	0.0486 (6)	0.0477 (6)	0.0378 (6)	0.0020 (5)	0.0078 (4)	0.0023 (5)
S2	0.0572 (7)	0.0670 (8)	0.0452 (6)	0.0120 (6)	0.0114 (5)	−0.0085 (5)
O1	0.0601 (19)	0.057 (2)	0.059 (2)	−0.0078 (15)	0.0119 (15)	−0.0071 (15)
O2	0.070 (2)	0.072 (2)	0.0449 (18)	0.0156 (17)	0.0139 (15)	0.0183 (16)
O3	0.059 (2)	0.068 (2)	0.088 (3)	0.0044 (18)	0.0237 (18)	0.0185 (19)
N1	0.049 (2)	0.039 (2)	0.049 (2)	0.0029 (16)	0.0122 (17)	−0.0008 (15)
N2	0.0460 (19)	0.046 (2)	0.0420 (19)	0.0047 (16)	0.0111 (16)	−0.0001 (15)
N3	0.0411 (18)	0.049 (2)	0.042 (2)	0.0083 (16)	0.0061 (15)	0.0010 (16)
C1	0.039 (2)	0.041 (2)	0.044 (2)	0.0106 (17)	0.0078 (17)	0.0082 (18)
C2	0.057 (3)	0.042 (2)	0.053 (3)	0.007 (2)	0.015 (2)	0.014 (2)
C3	0.058 (3)	0.041 (2)	0.055 (3)	0.011 (2)	0.018 (2)	0.002 (2)
C4	0.046 (2)	0.056 (3)	0.043 (2)	0.019 (2)	0.0111 (18)	0.002 (2)
C5	0.079 (3)	0.058 (3)	0.052 (3)	0.013 (2)	0.030 (2)	0.017 (2)
C6	0.077 (3)	0.037 (2)	0.056 (3)	0.006 (2)	0.025 (2)	0.010 (2)
C7	0.038 (2)	0.046 (2)	0.039 (2)	0.0147 (18)	0.0014 (17)	0.0022 (18)
C8	0.044 (2)	0.060 (3)	0.057 (3)	0.020 (2)	0.011 (2)	0.014 (2)
C9	0.056 (3)	0.080 (3)	0.052 (3)	0.027 (2)	0.021 (2)	0.013 (2)
Cl2	0.0968 (10)	0.0802 (10)	0.0634 (8)	0.0332 (8)	0.0091 (7)	0.0040 (7)
S3	0.0483 (6)	0.0431 (6)	0.0643 (7)	0.0136 (5)	0.0182 (5)	0.0104 (5)
S4	0.0632 (7)	0.0641 (8)	0.0448 (6)	0.0112 (6)	0.0121 (5)	−0.0066 (5)
O4	0.0518 (18)	0.073 (2)	0.084 (2)	0.0203 (16)	0.0285 (17)	0.0204 (19)
O5	0.084 (2)	0.0379 (17)	0.087 (3)	0.0158 (16)	0.0302 (19)	0.0047 (16)
O6	0.097 (3)	0.066 (2)	0.071 (2)	0.021 (2)	0.028 (2)	0.0261 (19)
N4	0.052 (2)	0.041 (2)	0.050 (2)	0.0078 (17)	0.0055 (16)	−0.0003 (16)
N5	0.052 (2)	0.044 (2)	0.042 (2)	0.0137 (16)	0.0069 (16)	0.0037 (16)
N6	0.057 (2)	0.051 (2)	0.0315 (18)	0.0168 (17)	0.0033 (16)	0.0056 (16)
C10	0.038 (2)	0.039 (2)	0.058 (3)	0.0082 (18)	0.0031 (18)	0.0137 (19)
C11	0.056 (3)	0.050 (3)	0.061 (3)	−0.003 (2)	0.008 (2)	0.020 (2)
C12	0.059 (3)	0.039 (3)	0.068 (3)	−0.001 (2)	−0.006 (2)	0.013 (2)
C13	0.057 (3)	0.047 (3)	0.058 (3)	0.021 (2)	0.001 (2)	0.014 (2)
C14	0.057 (3)	0.059 (3)	0.063 (3)	0.007 (2)	0.017 (2)	0.015 (2)
C15	0.043 (2)	0.047 (3)	0.072 (3)	0.0000 (19)	0.016 (2)	0.006 (2)
C16	0.038 (2)	0.050 (3)	0.040 (2)	0.0146 (18)	0.0011 (17)	0.0015 (19)
C17	0.052 (3)	0.072 (3)	0.047 (3)	0.016 (2)	0.010 (2)	0.011 (2)
C18	0.072 (3)	0.073 (3)	0.049 (3)	0.016 (3)	0.018 (2)	0.011 (2)
O7	0.077 (3)	0.065 (2)	0.093 (3)	0.030 (2)	0.013 (2)	0.0167 (19)
O8	0.056 (2)	0.146 (5)	0.131 (4)	0.030 (3)	0.029 (3)	0.013 (3)

Geometric parameters (Å, º) top

Cl1—C4	1.744 (4)	S3—O5	1.441 (3)
S1—O1	1.422 (3)	S3—N4	1.649 (4)
S1—O2	1.438 (3)	S3—C10	1.759 (5)
S1—N1	1.644 (4)	S4—C16	1.746 (4)
S1—C1	1.770 (4)	S4—C18	1.812 (5)
S2—C7	1.741 (4)	O6—C17	1.218 (6)
S2—C9	1.808 (5)	N4—N5	1.442 (5)
O3—C8	1.202 (5)	N4—H4N	0.850 (19)
N1—N2	1.440 (5)	N5—C16	1.276 (5)
N1—H1N	0.842 (19)	N6—C17	1.353 (6)
N2—C7	1.285 (5)	N6—C16	1.381 (5)
N3—C7	1.370 (5)	N6—H6N	0.851 (19)
N3—C8	1.374 (5)	C10—C11	1.389 (6)
N3—H3N	0.851 (19)	C10—C15	1.390 (6)
C1—C6	1.377 (6)	C11—C12	1.369 (7)
C1—C2	1.385 (6)	C11—H11	0.9300
C2—C3	1.389 (6)	C12—C13	1.368 (6)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.366 (6)	C13—C14	1.380 (6)
C3—H3	0.9300	C14—C15	1.368 (6)
C4—C5	1.379 (6)	C14—H14	0.9300
C5—C6	1.381 (6)	C15—H15	0.9300
C5—H5	0.9300	C17—C18	1.498 (7)
C6—H6	0.9300	C18—H18A	0.9700
C8—C9	1.503 (6)	C18—H18B	0.9700
C9—H9A	0.9700	O7—H71	0.82 (2)
C9—H9B	0.9700	O7—H72	0.82 (2)
Cl2—C13	1.737 (5)	O8—H81	0.82 (2)
S3—O4	1.426 (3)	O8—H82	0.83 (2)

O1—S1—O2	120.4 (2)	O4—S3—N4	107.3 (2)
O1—S1—N1	105.18 (19)	O5—S3—N4	103.2 (2)
O2—S1—N1	105.77 (19)	O4—S3—C10	107.8 (2)
O1—S1—C1	108.45 (19)	O5—S3—C10	108.6 (2)
O2—S1—C1	107.88 (19)	N4—S3—C10	109.61 (18)
N1—S1—C1	108.64 (18)	C16—S4—C18	91.4 (2)
C7—S2—C9	91.4 (2)	N5—N4—S3	112.3 (3)
N2—N1—S1	113.6 (3)	N5—N4—H4N	106 (3)
N2—N1—H1N	106 (3)	S3—N4—H4N	97 (3)
S1—N1—H1N	107 (3)	C16—N5—N4	112.6 (3)
C7—N2—N1	111.2 (3)	C17—N6—C16	117.8 (4)
C7—N3—C8	117.6 (4)	C17—N6—H6N	124 (3)
C7—N3—H3N	122 (3)	C16—N6—H6N	117 (3)
C8—N3—H3N	119 (3)	C11—C10—C15	119.4 (4)
C6—C1—C2	120.4 (4)	C11—C10—S3	120.0 (3)
C6—C1—S1	119.8 (3)	C15—C10—S3	120.6 (3)
C2—C1—S1	119.8 (3)	C12—C11—C10	120.1 (4)
C1—C2—C3	119.6 (4)	C12—C11—H11	119.9
C1—C2—H2	120.2	C10—C11—H11	119.9
C3—C2—H2	120.2	C13—C12—C11	119.7 (4)
C4—C3—C2	119.0 (4)	C13—C12—H12	120.1
C4—C3—H3	120.5	C11—C12—H12	120.1
C2—C3—H3	120.5	C12—C13—C14	121.2 (5)
C3—C4—C5	122.1 (4)	C12—C13—Cl2	119.4 (4)
C3—C4—Cl1	118.6 (3)	C14—C13—Cl2	119.4 (4)
C5—C4—Cl1	119.2 (3)	C15—C14—C13	119.4 (4)
C4—C5—C6	118.7 (4)	C15—C14—H14	120.3
C4—C5—H5	120.7	C13—C14—H14	120.3
C6—C5—H5	120.7	C14—C15—C10	120.3 (4)
C1—C6—C5	120.2 (4)	C14—C15—H15	119.9
C1—C6—H6	119.9	C10—C15—H15	119.9
C5—C6—H6	119.9	N5—C16—N6	118.7 (4)
N2—C7—N3	119.3 (4)	N5—C16—S4	129.9 (3)
N2—C7—S2	128.6 (3)	N6—C16—S4	111.3 (3)
N3—C7—S2	112.1 (3)	O6—C17—N6	124.2 (4)
O3—C8—N3	123.9 (4)	O6—C17—C18	124.6 (4)
O3—C8—C9	125.7 (4)	N6—C17—C18	111.2 (4)
N3—C8—C9	110.4 (4)	C17—C18—S4	108.0 (3)
C8—C9—S2	108.4 (3)	C17—C18—H18A	110.1
C8—C9—H9A	110.0	S4—C18—H18A	110.1
S2—C9—H9A	110.0	C17—C18—H18B	110.1
C8—C9—H9B	110.0	S4—C18—H18B	110.1
S2—C9—H9B	110.0	H18A—C18—H18B	108.4
H9A—C9—H9B	108.4	H71—O7—H72	98 (6)
O4—S3—O5	119.9 (2)	H81—O8—H82	94 (7)

O1—S1—N1—N2	172.9 (3)	O4—S3—N4—N5	−59.2 (3)
O2—S1—N1—N2	−58.6 (3)	O5—S3—N4—N5	173.2 (3)
C1—S1—N1—N2	57.0 (3)	C10—S3—N4—N5	57.6 (3)
S1—N1—N2—C7	111.8 (3)	S3—N4—N5—C16	109.7 (3)
O1—S1—C1—C6	−22.2 (4)	O4—S3—C10—C11	23.0 (4)
O2—S1—C1—C6	−154.2 (4)	O5—S3—C10—C11	154.4 (3)
N1—S1—C1—C6	91.6 (4)	N4—S3—C10—C11	−93.5 (4)
O1—S1—C1—C2	158.0 (3)	O4—S3—C10—C15	−157.6 (3)
O2—S1—C1—C2	26.0 (4)	O5—S3—C10—C15	−26.3 (4)
N1—S1—C1—C2	−88.2 (4)	N4—S3—C10—C15	85.8 (4)
C6—C1—C2—C3	−1.2 (6)	C15—C10—C11—C12	−0.4 (7)
S1—C1—C2—C3	178.6 (3)	S3—C10—C11—C12	179.0 (4)
C1—C2—C3—C4	−0.1 (6)	C10—C11—C12—C13	0.6 (7)
C2—C3—C4—C5	1.2 (7)	C11—C12—C13—C14	0.2 (7)
C2—C3—C4—Cl1	−177.7 (3)	C11—C12—C13—Cl2	−179.1 (3)
C3—C4—C5—C6	−1.1 (7)	C12—C13—C14—C15	−1.2 (7)
Cl1—C4—C5—C6	177.9 (4)	Cl2—C13—C14—C15	178.1 (4)
C2—C1—C6—C5	1.4 (7)	C13—C14—C15—C10	1.3 (7)
S1—C1—C6—C5	−178.4 (4)	C11—C10—C15—C14	−0.6 (7)
C4—C5—C6—C1	−0.3 (7)	S3—C10—C15—C14	−179.9 (4)
N1—N2—C7—N3	−176.1 (3)	N4—N5—C16—N6	−179.6 (3)
N1—N2—C7—S2	5.0 (5)	N4—N5—C16—S4	0.8 (5)
C8—N3—C7—N2	178.3 (4)	C17—N6—C16—N5	−174.4 (4)
C8—N3—C7—S2	−2.6 (5)	C17—N6—C16—S4	5.3 (5)
C9—S2—C7—N2	−179.0 (4)	C18—S4—C16—N5	174.5 (4)
C9—S2—C7—N3	2.0 (3)	C18—S4—C16—N6	−5.1 (3)
C7—N3—C8—O3	−178.6 (4)	C16—N6—C17—O6	177.6 (4)
C7—N3—C8—C9	1.6 (5)	C16—N6—C17—C18	−2.1 (5)
O3—C8—C9—S2	−179.7 (4)	O6—C17—C18—S4	178.5 (4)
N3—C8—C9—S2	0.0 (5)	N6—C17—C18—S4	−1.8 (5)
C7—S2—C9—C8	−1.1 (3)	C16—S4—C18—C17	3.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O7ⁱ	0.84 (2)	2.07 (2)	2.900 (6)	168 (4)
N3—H3N···N5ⁱⁱ	0.85 (2)	2.07 (2)	2.895 (5)	162 (4)
C9—H9B···O2ⁱⁱ	0.97	2.42	3.236 (6)	141
N4—H4N···O8	0.85 (2)	1.95 (2)	2.788 (6)	168 (4)
N6—H6N···N2ⁱⁱⁱ	0.85 (2)	1.97 (2)	2.808 (5)	170 (4)
C15—H15···O1^iv	0.93	2.55	3.355 (5)	145
O7—H71···O5	0.82 (2)	2.08 (3)	2.868 (5)	162 (6)
O7—H72···O6^iv	0.82 (2)	1.99 (2)	2.810 (5)	174 (6)
O8—H81···O4ⁱⁱ	0.82 (2)	2.35 (6)	2.987 (6)	136 (7)
O8—H81···O7ⁱⁱ	0.82 (2)	2.50 (7)	3.034 (7)	124 (7)
O8—H82···O3ⁱⁱⁱ	0.83 (2)	2.37 (3)	3.159 (7)	159 (8)

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

Acknowledgements

The authors thank the SAIF, Panjab University, for use of the NMR facility.

Funding information

NP thanks the Department of Science and Technology, Government of India, New Delhi, for a research fellowship under its PURSE Program and BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under a UGC–BSR one-time grant to faculty.

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