Synthesis, crystal structure and Hirshfeld surface analysis of N-(4-fluoro­phen­yl)-N-isopropyl-2-(methyl­sulfon­yl)acetamide

Geetha, D.; Anil Kumar, H.G.; Mohan Kumar, T.M.; Srinivasa, G.R.; Basavaraju, Y.B.; Yathirajan, H.S.; Parkin, S.

doi:10.1107/S2056989023003675

research communications

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ISSN: 2056-9890

Volume 79| Part 5| May 2023| Pages 512-515

https://doi.org/10.1107/S2056989023003675

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Synthesis, crystal structure and Hirshfeld surface analysis of N-(4-fluorophenyl)-N-isopropyl-2-(methylsulfonyl)acetamide

Doreswamy Geetha,^a Haleyur G. Anil Kumar,^b Thaluru M. Mohan Kumar,^c Gejjalagere R. Srinivasa,^d Yeriyur B. Basavaraju,^a ^* Hemmige S. Yathirajan ^a ^* and Sean Parkin ^e

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, ^bDepartment of Science and Humanities, PES University, BSK III Stage, Bengaluru-560 085, India, ^cDepartment of Chemistry, Amrita School of Engineering, Amrita Vishwa Vidyapeetham, Bengaluru-560 035, India, ^dHoneychem Pharma Research Pvt. Ltd., Peenya Industrial Area, Bengaluru-560 058, India, and ^eDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
^*Correspondence e-mail: ybb2706@gmail.com, yathirajan@hotmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 13 April 2023; accepted 22 April 2023; online 28 April 2023)

The synthesis and crystal structure of the title compound, C₁₂H₁₆FNO₃S, which is related to the herbicide flufenacet, are presented. The dihedral angle between the amide group and the fluorinated benzene ring is 87.30 (5)° and the N—C—C—S torsion angle defining the orientation of the methylsulfonyl substituent relative to the amide group is 106.91 (11)°. In the crystal, inversion-related molecules form dimers as a result of pairwise C—H⋯O hydrogen bonds, which appear to be reinforced by short O⋯π contacts [O⋯Cg = 3.0643 (11) Å]. A Hirshfeld surface analysis was used to quantify the various types of intermolecular contacts, which are dominated by H atoms.

Keywords: N-(substituted phenyl)acetamide; flufenacet metabolite; crystal structure; Hirshfeld surface analysis.

CCDC reference: 2258160

1. Chemical context

N-(Substituted phenyl)acetamides have a variety of biological activities. For example, substituted phenylacetamides and their use as protease inhibitors was reported by Kreutter et al. (2009 ) and a description of the syntheses and antioxidant studies of N-substituted benzyl/phenyl-2-[3,4-dimethyl-5,5-dioxidopyrazolo[4,3-c][1,2]benzothiazin-2(4H)-yl]acetamides was given by Ahmad et al. (2013 ). The syntheses and biological evaluation of N⁴-substituted sulfonamide–acetamide derivatives as dihydrofolate reductase (DHFR) inhibitors was reported by Hussein et al. (2019 ) and the synthesis of N-(substituted phenyl)-N-(substituted)acetamide derivatives as potent analgesic agents was described by Verma et al. (2020 ). Lastly, the evaluation of new 2-hydroxy-N-(4-oxo-2-substituted phenyl-1,3-thiazolidin-3-yl)-2-phenylacetamide derivatives as potential antimycobacterial agents was reported by Güzel-Akdemir et al. (2020 ).

Flufenacet (C₁₄H₁₃F₄N₃O₂S), systematic name N-(4-fluorophenyl)-N-propan-2-yl-2-{[5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl]oxy}acetamide, is an herbicide, xenobiotic and environmental contaminant (Rouchaud et al., 2001 ; Zimmerman et al., 2002 ). This paper reports the synthesis, crystal structure and a Hirshfeld surface analysis of the related title compound, C₁₂H₁₆FNO₃S (I) (Fig. 1).

Figure 1
The molecular structure of I showing 50% displacement ellipsoids.

2. Structural commentary

In the crystal structure of I, the nitrogen atom of the amide group is close to planar, the sum of bond angles about N1 being 358.92 (19)°, which places N1 0.0862 (14) Å from the plane passing through C1, C4, and C7. The amide group is also almost planar, having an r.m.s. deviation from the mean plane of N1, C1, O1, C2 of 0.0095 Å [maximum = 0.0165 (11) Å for C1], and is almost perpendicular to the fluorobenzene ring (C7–C12), subtending a dihedral angle of 87.30 (5)°. The overall conformation of the molecule is defined by the torsion angles C7—N1—C1—C2 [14.68 (17)°], N1—C1—C2—S1 [106.91 (11)°], C1—C2—S1—C3 [74.53 (10)°] and by the orientation of the ⁱpropyl group, e.g., C1—N1—C4—C6 [139.85 (13)°]. Otherwise, all bond lengths and angles lie within the expected ranges.

3. Supramolecular features

There are no strong hydrogen bonds in the crystal structure of I (Fig. 2), but there are a number of weaker C—H⋯O and C—H⋯F interactions, which are quantified in Table 1. The most prominent supramolecular constructs are dimers in which inversion-related molecules are linked by C2—H2A⋯O3ⁱ and C2ⁱ—H2Aⁱ⋯O3 hydrogen bonds [symmetry code: (i) 1 – x, 1 – y, 1 – z]. These dimers also feature close contacts between the sulfone O3 atom and the inversion-related benzene ring to give an O3⋯Cg(C7–C12)ⁱ distance of 3.0643 (11) Å (e.g. Gung et al., 2008 and see also Section 4: Database survey). The other weak C—H⋯O interactions involve inversion, translation, and c-glide related molecules (Table 1, Fig. 3a). A Hirshfeld surface analysis using CrystalExplorer (Spackman et al., 2021 ) shows that almost all atom–atom contacts involve the hydrogen atoms (Fig. 3b–f).

Table 1
Weak hydrogen bonds and other short intermolecular contacts (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O3ⁱ	0.99	2.31	3.2025 (16)	150
C3—H3B⋯O1ⁱⁱ	0.98	2.55	3.5196 (17)	170
C5—H5A⋯F1ⁱⁱⁱ	0.98	2.50	3.4295 (18)	158
C11—H11⋯O1^iv	0.95	2.39	3.1851 (16)	141
C12—H12⋯O2^iv	0.95	2.56	3.2955 (16)	134
O3⋯Cg(C7–C12)ⁱ			3.0643 (11)
Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 1, −y, −z + 1; (iii) x, y − 1, z; (iv) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .

Figure 2
A partial packing plot of I, showing inversion dimers resulting from pairs of C—H⋯O weak hydrogen bonds, augmented by O⋯Cg(ring) contacts. Hydrogen atoms not involved in the hydrogen bonds are omitted.

Figure 3
(a) The Hirshfeld surface of I expressed over d_norm, with C—H⋯O and C—H⋯F interactions drawn as dashed lines and as dark- and light-red regions on the Hirshfeld surface, respectively; (b) fingerprint plot of H⋯H contacts; (c) H⋯O/O⋯H contacts; (d) H⋯F/F⋯H contacts; (e) H⋯C/C⋯H contacts; (f) C⋯O/O⋯C contacts.

4. Database survey

A search of the Cambridge Structural Database (CSD, v5.43 with updates through November 2022; Groom et al., 2016 ) for a molecular fragment consisting of N-phenylacetamide with `any non-H group' attached at the nitrogen atom, the 4-position of the benzene ring, and replacing one hydrogen of the methyl group, yielded 259 hits. A similar fragment, but with `any halogen' at the 4-position on the ring, gave 92 hits. With the halogen restricted to fluorine, twelve hits were returned, and with an isopropyl group attached to the nitrogen atom, only one match was found: CSD refcode QEMHOG (Gao & Ng, 2006 ): this structure has a 1,3-benzothiazol-2-yl-oxy group attached to the methylene carbon atom of the search fragment.

A search of the CSD for non-bonded close contacts (up to 3.1Å) between S=O oxygen atoms and a benzene-ring centroid (with `any substituent') returned 154 hits, none of which have much else in common with I. A crystallographic and computational study of interactions between oxygen lone pairs and aromatic rings (albeit involving carbon-bound oxygen atoms) was presented by Gung et al. (2008).

There are several other related structures in the CSD, namely: thiamphenicol, D-threo-2,2-dichloro-N-{2-hydroxy-1-(hydroxymethyl)-2-[4-(methylsulfonyl)phenyl]ethyl}acetamide (CABCIR01; Ghosh et al., 1987 ), 2,2-dichloro-N-{[1-(fluoromethyl)-2-hydroxy-2-[4- (methylsulfonyl)phenyl]ethyl}acetamide (GAWNIC; Cheng et al., 2005 ), N-(2,6-dimethylphenyl)-2-(2-{3-[4-(methylsulfonyl)phenyl]-1,2,4-oxadiazol-5-yl}phenoxy)acetamide (AFIFIF; Wang et al., 2007 ), N-(4-chloro-2-nitrophenyl)-N-(methylsulfonyl)acetamide (WOGWEV; Zia-ur-Rehman et al., 2008 ), N-(4-methoxy-2-nitro-phenyl)-N-(methylsulfonyl)acetamide (QOTNAP; Zia-ur-Rehman et al., 2009 ), 2-chloro-N-(4-chloro-2-(2-chlorobenzoyl)phenyl)acetamide (DUPLUW; Dutkiewicz et al., 2010 ), 2-chloro-N-[2-(2-fluorobenzoyl)-4-nitrophenyl]-N-methylacetamide (EXIVEN; Siddaraju et al., 2011 ), 2-phenyl-N-(pyrazin-2-yl)acetamide (ROJNAH; Nayak et al., 2014 ) and 2-(perfluorophenyl)acetamide (LAMRAW; Novikov et al., 2022 ).

5. Synthesis, crystallization and spectroscopic details

In a 250 ml flask (with a nitrogen inlet and a septum) was placed 5 g of 4-fluoro-N-isopropylbenzenamine dissolved in 50 ml of acetonitrile. After cooling to 273 K, 6.7 g of triethylamine and 4.11 g of 2-(methylthio)acetyl chloride were added. The mixture was stirred at room temperature for 5 h. After this, 100 ml of water were added and the mixture was extracted three times, each with 100 ml of methyl tert-butyl ether (MTBE). The combined organic phases were dried over MgSO₄ and the solvent was evaporated under reduced pressure. The crude product, N-(4-fluorophenyl)-N-isopropyl-2-(methylthio)acetamide, was used for the next stage with purification (7.5 g).

To a 250 ml round-bottomed flask (with a nitrogen inlet and a septum) was added 7.5 g of N-(4-fluorophenyl)-N-isopropyl-2-(methylthio)acetamide dissolved in 150 ml of dichloromethane. After cooling to 263–273 K, 13.37 g of meta-chloroperbenzoic acid in 100 ml dichloromethane was added slowly at the same temperature. The mixture was stirred at room temperature for 5 h. After this, 200 ml of water were added and the organic layer was separated, and washed with 100 ml of 10% sodium bicarbonate twice. The organic phases were dried over MgSO₄ and the solvent was evaporated under reduced pressure. The crude product was purified by chromatography over SiO₂ (hexane:ethyl acetate 9:1 v/v). The title compound was recrystallized from diethyl ether solution in the form of colorless plates. The overall reaction scheme is shown in Fig. 4.

Figure 4
A reaction scheme for the synthesis of I. DCM is dichloromethane, mCPBA is meta-chloroperbenzoic acid.

¹H NMR: CDCl₃ (400 MHz, δ ppm): 1.097–1.08 [6H, d, (CH₃)₂]; 3.198 (3H, s, –CH₃); 3.664 (2H, s, CH₂); 5.006–4.938 (1H, m, –CH); 7.273–7.132 (4H, m, ar H). MS m/z: 273.45 (M)⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were found in difference-Fourier maps, but subsequently included in the refinement using riding models, with constrained C—H distances set to 0.95 Å (Csp²H), 0.98 Å (RCH₃), 0.99 Å (R₂CH₂) and 1.00 Å (R₃CH). U_iso(H) parameters were set to values of either 1.2U_eq or 1.5U_eq (RCH₃ only) of the attached atom.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₆FNO₃S
M_r	273.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	90
a, b, c (Å)	12.9530 (3), 8.7657 (2), 11.7723 (3)
β (°)	100.457 (1)
V (Å³)	1314.45 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.32 × 0.31 × 0.09

Data collection
Diffractometer	Bruker D8 Venture dual source
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.833, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	22801, 3010, 2678
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.05
No. of reflections	3010
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.37
Computer programs: APEX3 (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), XP in SHELXTL (Sheldrick, 2008 ), CrystalExplorer (Spackman et al., 2021), SHELXTL (Sheldrick, 2008), and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2258160

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989023003675/hb8062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023003675/hb8062Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023003675/hb8062Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and CrystalExplorer (Spackman et al., 2021); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

N-(4-Fluorophenyl)-2-(methylsulfonyl)-N-(propan-2-yl)acetamide top

Crystal data top

C₁₂H₁₆FNO₃S	F(000) = 576
M_r = 273.32	D_x = 1.381 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.9530 (3) Å	Cell parameters from 9889 reflections
b = 8.7657 (2) Å	θ = 2.8–27.5°
c = 11.7723 (3) Å	µ = 0.26 mm⁻¹
β = 100.457 (1)°	T = 90 K
V = 1314.45 (5) Å³	Rounded plate, colourless
Z = 4	0.32 × 0.31 × 0.09 mm

Data collection top

Bruker D8 Venture dual source diffractometer	3010 independent reflections
Radiation source: microsource	2678 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm^-1	R_int = 0.030
φ and ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −16→16
T_min = 0.833, T_max = 0.971	k = −11→11
22801 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: difference Fourier map
wR(F²) = 0.079	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0327P)² + 0.7883P] where P = (F_o² + 2F_c²)/3
3010 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Special details top

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998).

Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

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

	x	y	z	U_iso*/U_eq
S1	0.54145 (2)	0.29322 (3)	0.38570 (3)	0.01394 (9)
F1	0.77308 (7)	0.83954 (10)	0.77262 (8)	0.0265 (2)
C1	0.70051 (10)	0.18349 (15)	0.54790 (11)	0.0153 (3)
N1	0.78957 (9)	0.26470 (13)	0.58233 (10)	0.0169 (2)
O1	0.69978 (7)	0.04745 (11)	0.52217 (8)	0.0193 (2)
C2	0.59691 (10)	0.26923 (15)	0.53498 (11)	0.0154 (3)
H2A	0.608749	0.370378	0.572495	0.018*
H2AB	0.547429	0.211700	0.573787	0.018*
O2	0.62454 (7)	0.33486 (11)	0.32511 (8)	0.0208 (2)
O3	0.45431 (7)	0.39662 (11)	0.38023 (8)	0.0201 (2)
C3	0.49181 (11)	0.11358 (15)	0.33711 (12)	0.0208 (3)
H3A	0.459299	0.120203	0.255330	0.031*
H3B	0.439182	0.081074	0.382298	0.031*
H3C	0.549247	0.039248	0.346600	0.031*
C9	0.7902 (1)	0.68848 (16)	0.61179 (12)	0.0191 (3)
H9	0.794529	0.777562	0.566931	0.023*
C8	0.79425 (10)	0.54409 (16)	0.56408 (12)	0.0188 (3)
H8	0.801145	0.533426	0.485496	0.023*
C7	0.7882 (1)	0.41507 (15)	0.63150 (11)	0.0154 (3)
C6	0.97208 (12)	0.2845 (2)	0.54665 (14)	0.0295 (3)
H6A	1.036051	0.225348	0.545252	0.044*
H6B	0.988878	0.372611	0.597886	0.044*
H6C	0.943028	0.319875	0.468411	0.044*
C5	0.93224 (12)	0.1303 (2)	0.71320 (14)	0.0309 (4)
H5A	0.877506	0.070798	0.740427	0.046*
H5B	0.950692	0.218725	0.763798	0.046*
H5C	0.994531	0.066468	0.714444	0.046*
C4	0.89195 (10)	0.18467 (16)	0.59065 (13)	0.0216 (3)
H4	0.880049	0.092462	0.539939	0.026*
C10	0.77975 (10)	0.69895 (15)	0.72594 (12)	0.0180 (3)
C11	0.77354 (10)	0.57396 (16)	0.79470 (11)	0.0174 (3)
H11	0.766284	0.585728	0.873082	0.021*
C12	0.77814 (10)	0.42986 (15)	0.74673 (11)	0.0162 (3)
H12	0.774416	0.341486	0.792531	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01361 (16)	0.01232 (15)	0.01522 (16)	0.00096 (11)	0.00086 (11)	−0.00046 (11)
F1	0.0312 (5)	0.0167 (4)	0.0308 (5)	−0.0009 (3)	0.0033 (4)	−0.0072 (3)
C1	0.0176 (6)	0.0165 (6)	0.0114 (6)	0.0028 (5)	0.0012 (5)	0.0006 (5)
N1	0.0158 (5)	0.0159 (5)	0.0179 (5)	0.0033 (4)	0.0001 (4)	−0.0022 (4)
O1	0.0224 (5)	0.0142 (5)	0.0202 (5)	0.0033 (4)	0.0015 (4)	−0.0020 (4)
C2	0.0164 (6)	0.0151 (6)	0.0142 (6)	0.0012 (5)	0.0016 (5)	−0.0018 (5)
O2	0.0210 (5)	0.0217 (5)	0.0208 (5)	0.0013 (4)	0.0070 (4)	0.0049 (4)
O3	0.0170 (5)	0.0180 (5)	0.0237 (5)	0.0049 (4)	−0.0007 (4)	−0.0018 (4)
C3	0.0208 (7)	0.0155 (6)	0.0243 (7)	−0.0016 (5)	−0.0004 (5)	−0.0058 (5)
C9	0.0184 (6)	0.0176 (6)	0.0212 (7)	−0.0010 (5)	0.0030 (5)	0.0043 (5)
C8	0.0194 (6)	0.0220 (7)	0.0152 (6)	0.0020 (5)	0.0038 (5)	0.0017 (5)
C7	0.0124 (6)	0.0158 (6)	0.0171 (6)	0.0004 (5)	0.0002 (5)	−0.0017 (5)
C6	0.0227 (7)	0.0418 (9)	0.0258 (8)	0.0094 (7)	0.0093 (6)	0.0081 (7)
C5	0.0184 (7)	0.0345 (9)	0.0389 (9)	0.0043 (6)	0.0030 (6)	0.0195 (7)
C4	0.0155 (6)	0.0222 (7)	0.0258 (7)	0.0052 (5)	0.0003 (5)	−0.0036 (6)
C10	0.0147 (6)	0.0158 (6)	0.0227 (7)	−0.0007 (5)	0.0010 (5)	−0.0035 (5)
C11	0.0148 (6)	0.0225 (7)	0.0148 (6)	−0.0027 (5)	0.0021 (5)	−0.0026 (5)
C12	0.0140 (6)	0.0181 (6)	0.0160 (6)	−0.0021 (5)	0.0010 (5)	0.0025 (5)

Geometric parameters (Å, º) top

S1—O3	1.4399 (9)	C9—H9	0.9500
S1—O2	1.4419 (10)	C8—C7	1.3920 (18)
S1—C3	1.7570 (13)	C8—H8	0.9500
S1—C2	1.7862 (13)	C7—C12	1.3922 (18)
F1—C10	1.3586 (15)	C6—C4	1.519 (2)
C1—O1	1.2300 (16)	C6—H6A	0.9800
C1—N1	1.3535 (17)	C6—H6B	0.9800
C1—C2	1.5213 (17)	C6—H6C	0.9800
N1—C7	1.4411 (16)	C5—C4	1.519 (2)
N1—C4	1.4876 (16)	C5—H5A	0.9800
C2—H2A	0.9900	C5—H5B	0.9800
C2—H2AB	0.9900	C5—H5C	0.9800
C3—H3A	0.9800	C4—H4	1.0000
C3—H3B	0.9800	C10—C11	1.3732 (19)
C3—H3C	0.9800	C11—C12	1.3892 (19)
C9—C10	1.378 (2)	C11—H11	0.9500
C9—C8	1.3896 (19)	C12—H12	0.9500

O3—S1—O2	117.90 (6)	C8—C7—C12	120.32 (12)
O3—S1—C3	108.18 (6)	C8—C7—N1	120.53 (12)
O2—S1—C3	109.13 (7)	C12—C7—N1	119.13 (12)
O3—S1—C2	106.87 (6)	C4—C6—H6A	109.5
O2—S1—C2	108.27 (6)	C4—C6—H6B	109.5
C3—S1—C2	105.84 (7)	H6A—C6—H6B	109.5
O1—C1—N1	123.48 (12)	C4—C6—H6C	109.5
O1—C1—C2	119.15 (12)	H6A—C6—H6C	109.5
N1—C1—C2	117.29 (11)	H6B—C6—H6C	109.5
C1—N1—C7	121.96 (11)	C4—C5—H5A	109.5
C1—N1—C4	118.22 (11)	C4—C5—H5B	109.5
C7—N1—C4	118.74 (11)	H5A—C5—H5B	109.5
C1—C2—S1	110.27 (9)	C4—C5—H5C	109.5
C1—C2—H2A	109.6	H5A—C5—H5C	109.5
S1—C2—H2A	109.6	H5B—C5—H5C	109.5
C1—C2—H2AB	109.6	N1—C4—C6	111.23 (12)
S1—C2—H2AB	109.6	N1—C4—C5	111.03 (12)
H2A—C2—H2AB	108.1	C6—C4—C5	111.49 (12)
S1—C3—H3A	109.5	N1—C4—H4	107.6
S1—C3—H3B	109.5	C6—C4—H4	107.6
H3A—C3—H3B	109.5	C5—C4—H4	107.6
S1—C3—H3C	109.5	F1—C10—C11	118.07 (12)
H3A—C3—H3C	109.5	F1—C10—C9	118.66 (12)
H3B—C3—H3C	109.5	C11—C10—C9	123.26 (12)
C10—C9—C8	118.19 (12)	C10—C11—C12	118.32 (12)
C10—C9—H9	120.9	C10—C11—H11	120.8
C8—C9—H9	120.9	C12—C11—H11	120.8
C9—C8—C7	119.96 (12)	C11—C12—C7	119.94 (12)
C9—C8—H8	120.0	C11—C12—H12	120.0
C7—C8—H8	120.0	C7—C12—H12	120.0

O1—C1—N1—C7	−168.59 (12)	C1—N1—C7—C12	78.93 (16)
C2—C1—N1—C7	14.68 (17)	C4—N1—C7—C12	−88.93 (15)
O1—C1—N1—C4	−0.67 (19)	C1—N1—C4—C6	139.85 (13)
C2—C1—N1—C4	−177.40 (11)	C7—N1—C4—C6	−51.84 (16)
O1—C1—C2—S1	−69.97 (14)	C1—N1—C4—C5	−95.38 (15)
N1—C1—C2—S1	106.91 (11)	C7—N1—C4—C5	72.93 (16)
O3—S1—C2—C1	−170.32 (9)	C8—C9—C10—F1	−178.38 (11)
O2—S1—C2—C1	−42.36 (11)	C8—C9—C10—C11	0.2 (2)
C3—S1—C2—C1	74.53 (10)	F1—C10—C11—C12	178.69 (11)
C10—C9—C8—C7	−0.3 (2)	C9—C10—C11—C12	0.1 (2)
C9—C8—C7—C12	−0.03 (19)	C10—C11—C12—C7	−0.36 (19)
C9—C8—C7—N1	178.39 (12)	C8—C7—C12—C11	0.34 (19)
C1—N1—C7—C8	−99.51 (15)	N1—C7—C12—C11	−178.10 (11)
C4—N1—C7—C8	92.63 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3ⁱ	0.99	2.31	3.2025 (16)	150
C3—H3B···O1ⁱⁱ	0.98	2.55	3.5196 (17)	170
C5—H5A···F1ⁱⁱⁱ	0.98	2.50	3.4295 (18)	158
C11—H11···O1^iv	0.95	2.39	3.1851 (16)	141
C12—H12···O2^iv	0.95	2.56	3.2955 (16)	134

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

Weak hydrogen bonds and other short intermolecular contacts (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3ⁱ	0.99	2.31	3.2025 (16)	150
C3—H3B···O1ⁱⁱ	0.98	2.55	3.5196 (17)	170
C5—H5A···F1ⁱⁱⁱ	0.98	2.50	3.4295 (18)	158
C11—H11···O1^iv	0.95	2.39	3.1851 (16)	141
C12—H12···O2^iv	0.95	2.56	3.2955 (16)	134
O3···Cg(C7–C12)ⁱ			3.0643 (11)

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

Acknowledgements

DG is grateful to the DOS in Chemistry, University of Mysore for providing research facilities. HSY thanks UGC for a BSR Faculty fellowship for three years.

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