(6-Fluoro-2-oxo-2H-chromen-4-yl)methyl di­ethyl­carbamodi­thio­ate

El-Khatatneh, N.; Chandra; Rajesh, B.M.; Kumar, S.; Doreswamy, B.H.; Mahendra, M.

doi:10.1107/S2414314616020691

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x162069

https://doi.org/10.1107/S2414314616020691

Open

access

(6-Fluoro-2-oxo-2H-chromen-4-yl)methyl diethylcarbamodithioate

Nasseem El-Khatatneh,^a Chandra,^a B. M. Rajesh,^b Shamantha Kumar,^c B. H. Doreswamy ^c and M. Mahendra ^a ^*

^aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, ^bDepartment of Physics, R. V. College of Engineering, Bangalore-560 059, India, and ^cDepartment of Physics, SJB Institute of Technology, Kengeri, Bangalore 560 060, India
^*Correspondence e-mail: mahendra@physics.uni-mysore.ac.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 27 December 2016; accepted 31 December 2016; online 6 January 2017)

The title compound, C₁₅H₁₆FNO₂S₂, crystallizes with two independent molecules (A and B) in the asymmetric unit. They differ essentially in the orientation of the ethyl groups. The chromene rings are planar (r.m.s. deviations = 0.013 Å for both molecules), with the maximum deviation from the ring planes being 0.014 (2) and 0.018 (2) Å for atoms C9A and C9B, respectively. The mean plane of the chromene ring makes dihedral angles of 80.01 (7) and 76.97 (8)° with the carbamodithioate moiety [(N—C(=S)—S] of molecules A and B, respectively. In the crystal, the two molecules are linked by C—H⋯S hydrogen bonds, forming a ladder-like arrangement propagating along the a-axis direction. Within the ladders there are offset π–π interactions involving the coumarins rings of the B molecules [intercentroid distances vary from 3.705 (2) to 3.860 (1) Å]. Neighbouring ladders are linked via offset π–π interactions involving the coumarins rings of the A molecules [intercentroid distances vary from 3.539 (1) to 3.601 (1) Å]. These latter interactions lead to the formation of layers parallel to the ac plane.

Keywords: crystal structure; chromene derivatives; carbamodithioate; hydrogen bonding; offset π–π interactions.

CCDC reference: 1525196

Structure description

Coumarins and their derivatives represent an interesting class of heterocyclic compounds, which have attracted attention because of their biological and medicinal properties, such as anti-bacterial (Basanagouda et al., 2009 ), anti-oxidant (Vukovic et al., 2010 ) and anti-inflammatory (Emmanuel-Giota et al., 2001 ). As part of our ongoing studies of coumarin derivatives (El-Khatatneh et al., 2016 ), the title compound was synthesized and we report herein on its crystal structure.

The title compound, Fig. 1, crystallized with two independent molecules (A and B) in the asymmetric unit. The coumarin units are planar with their maximum deviations being 0.014 (2) and 0.018 (2) Å, for atoms C9A and C9B, respectively. The mean plane of the chromene rings make dihedral angles of 80.01 (7) and 76.97 (8)° with the carbamodithioate moiety [(N—C(=S)—S] of molecules A and B, respectively. The AutoMolFit drawing, Fig. 2 (PLATON; Spek, 2009 ), illustrates that the main difference in the conformation of the two molecules concerns the orientation of the ethyl groups. They are present in -anti-periplanar (C14A–N1A–C11A–S1A) and -syn-periplanar (C14B–N1B–C11B–S1B) conformations with respect to the carbamodithioate moiety [(N—C(=S)—S].

Figure 1
The molecular structure of the two independent molecules of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
AutoMolFit drawing of molecule B (red) on molecule A (black) [PLATON; Spek, 2009

In the crystal, the two molecules are linked by a C—H⋯S hydrogen bond, and these units are linked by further C—H⋯S hydrogen bonds, forming a ladder-like arrangement propagating along the a-axis direction (Fig. 3 and Table 1). Within the ladders there are offset π-π interactions involving the coumarin rings of the B molecules [intercentroid distances vary from 3.705 (2) to 3.860 (1) Å]. Neighbouring ladders are linked by offset π–π interactions involving the coumarin rings of the A molecules [intercentroid distances vary from 3.539 (1) to 3.601 (1) Å], leading to the formation of layers parallel to the ac plane (Fig. 3 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10A—H10A⋯S2B	0.97	2.87	3.621 (2)	135
C12A—H13C⋯O2Bⁱ	0.97	2.60	3.368 (3)	136
C2B—H2B⋯S2Bⁱⁱ	0.93	2.87	3.693 (3)	148
C10B—H10C⋯S2Aⁱⁱⁱ	0.97	2.82	3.660 (2)	145
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z; (iii) x-1, y, z.

Figure 3
A view along the b axis of the crystal packing of the title compound, showing the hydrogen bonds as dashed lines (see Table 1

; molecule A blue, molecule B red). The H atoms not involved in hydrogen bonding have been omitted for clarity.

Synthesis and crystallization

4-Bromomethyl-6,7-dimethyl-chromen-2-one (3.9 g, 0.015 mol) and the potassium salt of morpholine-4-carboxylate 2.5 g (0.015 mol) were dissolved in 35 ml of absolute ethanol and stirred at room temperature for 14 h. After completion of the reaction (monitored by TLC), the ethanol was removed under reduced pressure. The solid obtained was extracted in ethyl acetate, washed with water, and the collected organic extract was dried over anhydrous Na₂SO₄. The solvent was removed under reduced pressure and the obtained solid product was recrystallized from an ethanol:chloroform mixture (7:3) by slow evaporation, giving colourless block-like crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₆FNO₂S₂
M_r	325.41
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.1284 (2), 12.2818 (3), 18.3709 (5)
α, β, γ (°)	75.625 (2), 88.538 (2), 86.553 (2)
V (Å³)	1555.10 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.36
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
No. of measured, independent and observed [I > 2σ(I)] reflections	18765, 4555, 3711
R_int	0.029
θ_max (°)	23.5
(sin θ/λ)_max (Å⁻¹)	0.560

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.03
No. of reflections	4555
No. of parameters	383
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.16
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS2016/6 (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009).

Structural data

CCDC reference: 1525196

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616020691/su4119sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020691/su4119Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2016/6 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016/6 (Sheldrick, 2015) and PLATON (Spek, 2009).

(6-Fluoro-2-oxo-2H-chromen-4-yl)methyl diethylcarbamodithioate top

Crystal data top

C₁₅H₁₆FNO₂S₂	Z = 4
M_r = 325.41	F(000) = 680
Triclinic, P1	D_x = 1.390 Mg m⁻³
a = 7.1284 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2818 (3) Å	Cell parameters from 4557 reflections
c = 18.3709 (5) Å	θ = 1.1–23.5°
α = 75.625 (2)°	µ = 0.36 mm⁻¹
β = 88.538 (2)°	T = 293 K
γ = 86.553 (2)°	Block, colourless
V = 1555.10 (7) Å³	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	3711 reflections with I > 2σ(I)
Radiation source: Bruker MicroStar microfocus rotating anode	R_int = 0.029
Detector resolution: 18.4 pixels mm^-1	θ_max = 23.5°, θ_min = 1.7°
φ and ω scans	h = −7→7
18765 measured reflections	k = −13→13
4555 independent reflections	l = −20→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0413P)² + 0.5771P] where P = (F_o² + 2F_c²)/3
4555 reflections	(Δ/σ)_max = 0.001
383 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.16 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
S1A	0.51933 (9)	0.66040 (5)	0.25174 (3)	0.05364 (19)
S2A	0.93545 (9)	0.68645 (6)	0.22242 (4)	0.0602 (2)
F1A	0.7749 (3)	0.18127 (14)	0.52266 (10)	0.0948 (6)
O1A	0.7712 (2)	0.62091 (17)	0.53152 (9)	0.0640 (5)
O2A	0.7301 (3)	0.80267 (19)	0.48010 (12)	0.0914 (7)
N1A	0.6629 (3)	0.83708 (15)	0.16329 (10)	0.0512 (5)
C1A	0.7756 (4)	0.2917 (2)	0.52380 (16)	0.0655 (7)
C2A	0.8280 (4)	0.3182 (3)	0.58777 (16)	0.0738 (9)
H2A	0.864836	0.261871	0.629689	0.089*
C3A	0.8258 (3)	0.4291 (3)	0.58945 (14)	0.0683 (8)
H3A	0.860317	0.449019	0.632678	0.082*
C4A	0.7714 (3)	0.5115 (2)	0.52580 (13)	0.0529 (6)
C5A	0.7216 (3)	0.4849 (2)	0.46005 (12)	0.0458 (6)
C6A	0.7236 (3)	0.3709 (2)	0.45985 (13)	0.0531 (6)
H6A	0.690296	0.349303	0.417061	0.064*
C7A	0.7241 (4)	0.7092 (2)	0.47157 (15)	0.0609 (7)
C8A	0.6733 (3)	0.6818 (2)	0.40312 (13)	0.0518 (6)
H8A	0.639944	0.740508	0.362011	0.062*
C9A	0.6715 (3)	0.57683 (19)	0.39565 (12)	0.0431 (5)
C10A	0.6263 (3)	0.54884 (18)	0.32320 (12)	0.0502 (6)
H10A	0.543009	0.487043	0.334541	0.060*
H10B	0.741791	0.522131	0.302691	0.060*
C11A	0.7138 (3)	0.73768 (18)	0.20824 (12)	0.0449 (5)
C12A	0.4672 (4)	0.8847 (2)	0.15371 (14)	0.0628 (7)
H13C	0.466889	0.965963	0.144464	0.075*
H13D	0.396879	0.856713	0.199792	0.075*
C13A	0.3726 (4)	0.8549 (3)	0.09011 (16)	0.0780 (8)
H14A	0.443735	0.880548	0.044619	0.117*
H14B	0.248238	0.890242	0.084249	0.117*
H14C	0.365089	0.774673	0.100622	0.117*
C14A	0.8042 (4)	0.9084 (2)	0.11895 (15)	0.0683 (7)
H15A	0.747783	0.953265	0.072877	0.082*
H15B	0.906248	0.861024	0.105437	0.082*
C15A	0.8818 (5)	0.9854 (3)	0.1617 (2)	0.0991 (11)
H16A	0.781020	1.032186	0.175377	0.149*
H16B	0.971273	1.031883	0.130680	0.149*
H16C	0.942355	0.941205	0.206303	0.149*
S1B	0.08922 (10)	0.33784 (6)	0.27010 (4)	0.0689 (2)
S2B	0.50869 (10)	0.28748 (6)	0.28251 (4)	0.0635 (2)
F1B	0.2068 (3)	0.76498 (13)	−0.04352 (10)	0.0965 (6)
O1B	0.2887 (2)	0.31283 (14)	−0.01045 (9)	0.0630 (5)
O2B	0.2880 (3)	0.13736 (16)	0.05644 (11)	0.0860 (6)
N1B	0.2507 (3)	0.15756 (16)	0.35756 (11)	0.0536 (5)
C1B	0.2303 (4)	0.6518 (2)	−0.03385 (16)	0.0628 (7)
C2B	0.2720 (4)	0.6108 (3)	−0.09550 (15)	0.0683 (8)
H2B	0.287050	0.659402	−0.142680	0.082*
C3B	0.2911 (4)	0.4965 (2)	−0.08610 (14)	0.0642 (7)
H3B	0.318233	0.466425	−0.127166	0.077*
C4B	0.2698 (3)	0.4262 (2)	−0.01553 (13)	0.0498 (6)
C5B	0.2303 (3)	0.46786 (18)	0.04738 (12)	0.0444 (5)
C6B	0.2095 (3)	0.5847 (2)	0.03657 (14)	0.0554 (6)
H6B	0.181708	0.616144	0.076986	0.067*
C7B	0.2686 (4)	0.2351 (2)	0.05671 (15)	0.0592 (7)
C8B	0.2283 (3)	0.2784 (2)	0.12185 (13)	0.0533 (6)
H8B	0.213405	0.227154	0.168002	0.064*
C9B	0.2111 (3)	0.38798 (19)	0.11955 (12)	0.0467 (6)
C10B	0.1792 (4)	0.4326 (2)	0.18835 (13)	0.0625 (7)
H10C	0.092746	0.498300	0.175431	0.075*
H10D	0.297740	0.457461	0.201271	0.075*
C11B	0.2913 (3)	0.25121 (19)	0.30801 (12)	0.0492 (6)
C12B	0.3993 (4)	0.0731 (2)	0.39041 (14)	0.0639 (7)
H13A	0.354027	0.026564	0.437468	0.077*
H13B	0.506735	0.111039	0.401320	0.077*
C13B	0.4604 (4)	−0.0008 (2)	0.33904 (19)	0.0854 (9)
H14D	0.355637	−0.040849	0.329730	0.128*
H14E	0.559207	−0.053535	0.362242	0.128*
H14F	0.505236	0.044952	0.292356	0.128*
C14B	0.0577 (4)	0.1330 (3)	0.38627 (17)	0.0811 (9)
H15C	0.062020	0.100211	0.440021	0.097*
H15D	−0.018925	0.202902	0.377820	0.097*
C15B	−0.0283 (5)	0.0566 (3)	0.3502 (3)	0.1224 (14)
H16D	−0.049498	0.093084	0.298224	0.184*
H16E	−0.146040	0.035520	0.374573	0.184*
H16F	0.053583	−0.009453	0.353828	0.184*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0565 (4)	0.0556 (4)	0.0454 (4)	−0.0069 (3)	−0.0087 (3)	−0.0041 (3)
S2A	0.0540 (4)	0.0632 (4)	0.0590 (4)	0.0101 (3)	−0.0035 (3)	−0.0097 (3)
F1A	0.1031 (13)	0.0625 (11)	0.0965 (13)	0.0007 (9)	0.0064 (10)	0.0206 (9)
O1A	0.0563 (11)	0.0928 (15)	0.0476 (10)	−0.0056 (10)	−0.0059 (8)	−0.0255 (10)
O2A	0.1197 (18)	0.0826 (15)	0.0881 (15)	−0.0025 (13)	−0.0183 (13)	−0.0506 (13)
N1A	0.0553 (12)	0.0455 (12)	0.0472 (11)	0.0008 (9)	−0.0059 (9)	−0.0015 (9)
C1A	0.0523 (16)	0.0660 (19)	0.0640 (18)	−0.0004 (13)	0.0059 (13)	0.0094 (14)
C2A	0.0516 (16)	0.091 (2)	0.0579 (18)	0.0019 (15)	0.0000 (13)	0.0195 (16)
C3A	0.0397 (14)	0.115 (3)	0.0403 (14)	−0.0060 (15)	−0.0021 (11)	−0.0011 (15)
C4A	0.0336 (12)	0.0764 (19)	0.0464 (14)	−0.0044 (12)	0.0021 (10)	−0.0112 (13)
C5A	0.0317 (12)	0.0623 (16)	0.0395 (13)	−0.0027 (10)	0.0037 (9)	−0.0057 (11)
C6A	0.0464 (14)	0.0574 (16)	0.0490 (14)	−0.0022 (11)	0.0060 (11)	−0.0016 (12)
C7A	0.0554 (16)	0.074 (2)	0.0613 (17)	−0.0032 (13)	−0.0038 (13)	−0.0307 (15)
C8A	0.0528 (14)	0.0580 (16)	0.0452 (14)	0.0011 (12)	−0.0044 (11)	−0.0146 (12)
C9A	0.0369 (12)	0.0501 (14)	0.0425 (13)	−0.0020 (10)	0.0010 (9)	−0.0118 (11)
C10A	0.0648 (15)	0.0426 (13)	0.0411 (13)	−0.0041 (11)	−0.0027 (11)	−0.0062 (10)
C11A	0.0560 (14)	0.0460 (14)	0.0349 (12)	−0.0011 (11)	−0.0044 (10)	−0.0142 (10)
C12A	0.0674 (17)	0.0550 (16)	0.0600 (16)	0.0104 (13)	−0.0074 (13)	−0.0053 (13)
C13A	0.0691 (18)	0.084 (2)	0.079 (2)	0.0074 (16)	−0.0180 (15)	−0.0169 (16)
C14A	0.0732 (18)	0.0617 (17)	0.0591 (16)	−0.0083 (14)	−0.0017 (14)	0.0069 (13)
C15A	0.113 (3)	0.070 (2)	0.113 (3)	−0.0313 (19)	0.000 (2)	−0.0137 (19)
S1B	0.0736 (5)	0.0745 (5)	0.0507 (4)	0.0198 (4)	0.0048 (3)	−0.0070 (3)
S2B	0.0661 (4)	0.0624 (4)	0.0603 (4)	−0.0193 (3)	−0.0007 (3)	−0.0083 (3)
F1B	0.1369 (16)	0.0513 (10)	0.0896 (12)	−0.0101 (10)	−0.0252 (11)	0.0084 (9)
O1B	0.0764 (12)	0.0585 (12)	0.0570 (11)	0.0061 (9)	0.0007 (9)	−0.0222 (9)
O2B	0.1241 (18)	0.0530 (12)	0.0868 (15)	0.0044 (11)	0.0041 (12)	−0.0310 (11)
N1B	0.0550 (12)	0.0524 (12)	0.0496 (12)	−0.0057 (10)	0.0022 (9)	−0.0049 (10)
C1B	0.0637 (17)	0.0488 (16)	0.0674 (19)	−0.0073 (12)	−0.0173 (14)	0.0045 (14)
C2B	0.0614 (17)	0.080 (2)	0.0524 (17)	−0.0100 (15)	−0.0029 (13)	0.0064 (15)
C3B	0.0597 (16)	0.080 (2)	0.0492 (15)	0.0024 (14)	0.0032 (12)	−0.0117 (14)
C4B	0.0409 (13)	0.0590 (16)	0.0486 (14)	0.0002 (11)	−0.0027 (10)	−0.0119 (12)
C5B	0.0394 (12)	0.0443 (14)	0.0486 (14)	−0.0018 (10)	−0.0085 (10)	−0.0093 (11)
C6B	0.0592 (15)	0.0508 (15)	0.0548 (15)	−0.0022 (12)	−0.0127 (12)	−0.0093 (12)
C7B	0.0660 (17)	0.0523 (17)	0.0610 (17)	0.0010 (13)	−0.0027 (13)	−0.0179 (14)
C8B	0.0639 (16)	0.0459 (15)	0.0489 (14)	−0.0005 (12)	−0.0024 (12)	−0.0102 (11)
C9B	0.0485 (13)	0.0459 (14)	0.0454 (13)	0.0021 (11)	−0.0061 (10)	−0.0111 (11)
C10B	0.093 (2)	0.0445 (14)	0.0479 (14)	0.0116 (13)	−0.0083 (13)	−0.0102 (12)
C11B	0.0638 (15)	0.0485 (14)	0.0370 (12)	−0.0019 (11)	0.0012 (11)	−0.0142 (11)
C12B	0.0710 (17)	0.0528 (16)	0.0603 (16)	−0.0026 (13)	−0.0061 (13)	0.0008 (13)
C13B	0.087 (2)	0.0594 (18)	0.111 (3)	0.0054 (16)	−0.0021 (19)	−0.0241 (18)
C14B	0.077 (2)	0.085 (2)	0.075 (2)	−0.0137 (17)	0.0029 (16)	−0.0034 (17)
C15B	0.083 (2)	0.120 (3)	0.170 (4)	−0.020 (2)	−0.015 (3)	−0.042 (3)

Geometric parameters (Å, º) top

S1A—C11A	1.785 (2)	S1B—C11B	1.787 (2)
S1A—C10A	1.793 (2)	S1B—C10B	1.787 (3)
S2A—C11A	1.668 (2)	S2B—C11B	1.662 (3)
F1A—C1A	1.362 (3)	F1B—C1B	1.357 (3)
O1A—C7A	1.373 (3)	O1B—C7B	1.370 (3)
O1A—C4A	1.374 (3)	O1B—C4B	1.371 (3)
O2A—C7A	1.200 (3)	O2B—C7B	1.202 (3)
N1A—C11A	1.329 (3)	N1B—C11B	1.320 (3)
N1A—C14A	1.468 (3)	N1B—C12B	1.467 (3)
N1A—C12A	1.477 (3)	N1B—C14B	1.481 (3)
C1A—C2A	1.362 (4)	C1B—C6B	1.360 (3)
C1A—C6A	1.369 (3)	C1B—C2B	1.369 (4)
C2A—C3A	1.368 (4)	C2B—C3B	1.371 (4)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.389 (3)	C3B—C4B	1.378 (3)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.387 (3)	C4B—C5B	1.391 (3)
C5A—C6A	1.400 (3)	C5B—C6B	1.399 (3)
C5A—C9A	1.453 (3)	C5B—C9B	1.449 (3)
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—C8A	1.440 (3)	C7B—C8B	1.441 (3)
C8A—C9A	1.331 (3)	C8B—C9B	1.334 (3)
C8A—H8A	0.9300	C8B—H8B	0.9300
C9A—C10A	1.502 (3)	C9B—C10B	1.504 (3)
C10A—H10A	0.9700	C10B—H10C	0.9700
C10A—H10B	0.9700	C10B—H10D	0.9700
C12A—C13A	1.496 (4)	C12B—C13B	1.503 (4)
C12A—H13C	0.9700	C12B—H13A	0.9700
C12A—H13D	0.9700	C12B—H13B	0.9700
C13A—H14A	0.9600	C13B—H14D	0.9600
C13A—H14B	0.9600	C13B—H14E	0.9600
C13A—H14C	0.9600	C13B—H14F	0.9600
C14A—C15A	1.507 (4)	C14B—C15B	1.448 (4)
C14A—H15A	0.9700	C14B—H15C	0.9700
C14A—H15B	0.9700	C14B—H15D	0.9700
C15A—H16A	0.9600	C15B—H16D	0.9600
C15A—H16B	0.9600	C15B—H16E	0.9600
C15A—H16C	0.9600	C15B—H16F	0.9600

C11A—S1A—C10A	103.59 (11)	C11B—S1B—C10B	103.50 (12)
C7A—O1A—C4A	121.12 (19)	C7B—O1B—C4B	121.61 (19)
C11A—N1A—C14A	120.6 (2)	C11B—N1B—C12B	120.9 (2)
C11A—N1A—C12A	124.3 (2)	C11B—N1B—C14B	123.2 (2)
C14A—N1A—C12A	115.09 (19)	C12B—N1B—C14B	115.9 (2)
C2A—C1A—F1A	118.9 (2)	F1B—C1B—C6B	118.3 (3)
C2A—C1A—C6A	123.3 (3)	F1B—C1B—C2B	118.4 (2)
F1A—C1A—C6A	117.8 (3)	C6B—C1B—C2B	123.2 (3)
C1A—C2A—C3A	119.0 (3)	C1B—C2B—C3B	118.5 (2)
C1A—C2A—H2A	120.5	C1B—C2B—H2B	120.8
C3A—C2A—H2A	120.5	C3B—C2B—H2B	120.8
C2A—C3A—C4A	119.2 (3)	C2B—C3B—C4B	119.7 (3)
C2A—C3A—H3A	120.4	C2B—C3B—H3B	120.2
C4A—C3A—H3A	120.4	C4B—C3B—H3B	120.2
O1A—C4A—C5A	121.9 (2)	O1B—C4B—C3B	116.5 (2)
O1A—C4A—C3A	116.2 (2)	O1B—C4B—C5B	121.6 (2)
C5A—C4A—C3A	121.9 (3)	C3B—C4B—C5B	121.9 (2)
C4A—C5A—C6A	117.8 (2)	C4B—C5B—C6B	117.6 (2)
C4A—C5A—C9A	118.1 (2)	C4B—C5B—C9B	118.3 (2)
C6A—C5A—C9A	124.1 (2)	C6B—C5B—C9B	124.1 (2)
C1A—C6A—C5A	118.8 (3)	C1B—C6B—C5B	119.1 (2)
C1A—C6A—H6A	120.6	C1B—C6B—H6B	120.4
C5A—C6A—H6A	120.6	C5B—C6B—H6B	120.4
O2A—C7A—O1A	117.6 (2)	O2B—C7B—O1B	117.5 (2)
O2A—C7A—C8A	125.3 (3)	O2B—C7B—C8B	125.8 (2)
O1A—C7A—C8A	117.1 (2)	O1B—C7B—C8B	116.7 (2)
C9A—C8A—C7A	123.4 (2)	C9B—C8B—C7B	123.6 (2)
C9A—C8A—H8A	118.3	C9B—C8B—H8B	118.2
C7A—C8A—H8A	118.3	C7B—C8B—H8B	118.2
C8A—C9A—C5A	118.4 (2)	C8B—C9B—C5B	118.2 (2)
C8A—C9A—C10A	123.2 (2)	C8B—C9B—C10B	123.3 (2)
C5A—C9A—C10A	118.3 (2)	C5B—C9B—C10B	118.5 (2)
C9A—C10A—S1A	116.64 (16)	C9B—C10B—S1B	116.79 (18)
C9A—C10A—H10A	108.1	C9B—C10B—H10C	108.1
S1A—C10A—H10A	108.1	S1B—C10B—H10C	108.1
C9A—C10A—H10B	108.1	C9B—C10B—H10D	108.1
S1A—C10A—H10B	108.1	S1B—C10B—H10D	108.1
H10A—C10A—H10B	107.3	H10C—C10B—H10D	107.3
N1A—C11A—S2A	124.47 (18)	N1B—C11B—S2B	124.09 (19)
N1A—C11A—S1A	113.32 (17)	N1B—C11B—S1B	113.70 (18)
S2A—C11A—S1A	122.20 (13)	S2B—C11B—S1B	122.22 (14)
N1A—C12A—C13A	112.1 (2)	N1B—C12B—C13B	112.3 (2)
N1A—C12A—H13C	109.2	N1B—C12B—H13A	109.1
C13A—C12A—H13C	109.2	C13B—C12B—H13A	109.1
N1A—C12A—H13D	109.2	N1B—C12B—H13B	109.1
C13A—C12A—H13D	109.2	C13B—C12B—H13B	109.1
H13C—C12A—H13D	107.9	H13A—C12B—H13B	107.9
C12A—C13A—H14A	109.5	C12B—C13B—H14D	109.5
C12A—C13A—H14B	109.5	C12B—C13B—H14E	109.5
H14A—C13A—H14B	109.5	H14D—C13B—H14E	109.5
C12A—C13A—H14C	109.5	C12B—C13B—H14F	109.5
H14A—C13A—H14C	109.5	H14D—C13B—H14F	109.5
H14B—C13A—H14C	109.5	H14E—C13B—H14F	109.5
N1A—C14A—C15A	111.8 (2)	C15B—C14B—N1B	112.1 (3)
N1A—C14A—H15A	109.3	C15B—C14B—H15C	109.2
C15A—C14A—H15A	109.3	N1B—C14B—H15C	109.2
N1A—C14A—H15B	109.3	C15B—C14B—H15D	109.2
C15A—C14A—H15B	109.3	N1B—C14B—H15D	109.2
H15A—C14A—H15B	107.9	H15C—C14B—H15D	107.9
C14A—C15A—H16A	109.5	C14B—C15B—H16D	109.5
C14A—C15A—H16B	109.5	C14B—C15B—H16E	109.5
H16A—C15A—H16B	109.5	H16D—C15B—H16E	109.5
C14A—C15A—H16C	109.5	C14B—C15B—H16F	109.5
H16A—C15A—H16C	109.5	H16D—C15B—H16F	109.5
H16B—C15A—H16C	109.5	H16E—C15B—H16F	109.5

F1A—C1A—C2A—C3A	−178.9 (2)	F1B—C1B—C2B—C3B	−178.3 (2)
C6A—C1A—C2A—C3A	1.3 (4)	C6B—C1B—C2B—C3B	1.0 (4)
C1A—C2A—C3A—C4A	−0.4 (4)	C1B—C2B—C3B—C4B	−0.6 (4)
C7A—O1A—C4A—C5A	−1.0 (3)	C7B—O1B—C4B—C3B	−179.3 (2)
C7A—O1A—C4A—C3A	178.5 (2)	C7B—O1B—C4B—C5B	0.4 (3)
C2A—C3A—C4A—O1A	179.6 (2)	C2B—C3B—C4B—O1B	179.3 (2)
C2A—C3A—C4A—C5A	−0.9 (4)	C2B—C3B—C4B—C5B	−0.4 (4)
O1A—C4A—C5A—C6A	−179.19 (19)	O1B—C4B—C5B—C6B	−178.7 (2)
C3A—C4A—C5A—C6A	1.4 (3)	C3B—C4B—C5B—C6B	1.1 (3)
O1A—C4A—C5A—C9A	1.1 (3)	O1B—C4B—C5B—C9B	0.6 (3)
C3A—C4A—C5A—C9A	−178.3 (2)	C3B—C4B—C5B—C9B	−179.7 (2)
C2A—C1A—C6A—C5A	−0.9 (4)	F1B—C1B—C6B—C5B	179.0 (2)
F1A—C1A—C6A—C5A	179.4 (2)	C2B—C1B—C6B—C5B	−0.3 (4)
C4A—C5A—C6A—C1A	−0.5 (3)	C4B—C5B—C6B—C1B	−0.7 (3)
C9A—C5A—C6A—C1A	179.2 (2)	C9B—C5B—C6B—C1B	−179.9 (2)
C4A—O1A—C7A—O2A	−178.7 (2)	C4B—O1B—C7B—O2B	−179.8 (2)
C4A—O1A—C7A—C8A	0.6 (3)	C4B—O1B—C7B—C8B	−0.5 (3)
O2A—C7A—C8A—C9A	178.8 (3)	O2B—C7B—C8B—C9B	178.8 (3)
O1A—C7A—C8A—C9A	−0.5 (4)	O1B—C7B—C8B—C9B	−0.3 (4)
C7A—C8A—C9A—C5A	0.7 (3)	C7B—C8B—C9B—C5B	1.3 (4)
C7A—C8A—C9A—C10A	−177.4 (2)	C7B—C8B—C9B—C10B	−176.6 (2)
C4A—C5A—C9A—C8A	−0.9 (3)	C4B—C5B—C9B—C8B	−1.4 (3)
C6A—C5A—C9A—C8A	179.4 (2)	C6B—C5B—C9B—C8B	177.8 (2)
C4A—C5A—C9A—C10A	177.2 (2)	C4B—C5B—C9B—C10B	176.6 (2)
C6A—C5A—C9A—C10A	−2.5 (3)	C6B—C5B—C9B—C10B	−4.2 (3)
C8A—C9A—C10A—S1A	−14.5 (3)	C8B—C9B—C10B—S1B	−19.8 (3)
C5A—C9A—C10A—S1A	167.51 (16)	C5B—C9B—C10B—S1B	162.27 (17)
C11A—S1A—C10A—C9A	81.97 (19)	C11B—S1B—C10B—C9B	79.0 (2)
C14A—N1A—C11A—S2A	2.9 (3)	C12B—N1B—C11B—S2B	−4.5 (3)
C12A—N1A—C11A—S2A	−176.84 (18)	C14B—N1B—C11B—S2B	172.5 (2)
C14A—N1A—C11A—S1A	−175.79 (17)	C12B—N1B—C11B—S1B	175.80 (17)
C12A—N1A—C11A—S1A	4.4 (3)	C14B—N1B—C11B—S1B	−7.3 (3)
C10A—S1A—C11A—N1A	−167.43 (16)	C10B—S1B—C11B—N1B	−163.79 (17)
C10A—S1A—C11A—S2A	13.81 (17)	C10B—S1B—C11B—S2B	16.45 (18)
C11A—N1A—C12A—C13A	−91.7 (3)	C11B—N1B—C12B—C13B	−80.5 (3)
C14A—N1A—C12A—C13A	88.5 (3)	C14B—N1B—C12B—C13B	102.4 (3)
C11A—N1A—C14A—C15A	−89.1 (3)	C11B—N1B—C14B—C15B	101.2 (3)
C12A—N1A—C14A—C15A	90.7 (3)	C12B—N1B—C14B—C15B	−81.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10A—H10A···S2B	0.97	2.87	3.621 (2)	135
C12A—H13C···O2Bⁱ	0.97	2.60	3.368 (3)	136
C2B—H2B···S2Bⁱⁱ	0.93	2.87	3.693 (3)	148
C10B—H10C···S2Aⁱⁱⁱ	0.97	2.82	3.660 (2)	145

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

Acknowledgements

MM thanks the UGC, New Delhi, Government of India, for the award of project F. No. 41–920/2012(SR) from 25–07–2012.

Funding information

Funding for this research was provided by: University Grants Commission (award No. 41–920/2012(SR));

References

Basanagouda, M., Kulkarni, M. V., Sharma, D., Gupta, V. K., Pranesha Sandhyarani, P. & Rasal, V. P. (2009). J. Chem. Sci. 121, 485–495. CSD CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El-Khatatneh, N., Chandra, , Shamala, D., Shivashankar, K. & Mahendra, M. (2016). IUCrData, 1, x161989. Google Scholar
Emmanuel-Giota, A. A., Fylaktakidou, K. C., Litinas, K. E., Nicolaides, D. N. & Hadjipavlou-Litina, D. J. (2001). J. Heterocycl. Chem. 38, 717–722. CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vukovic, N., Sukdolak, S., Solujic, S. & Niciforovic, N. (2010). Arch. Pharm. Res. 33, 5–15. Web of Science CrossRef CAS PubMed Google Scholar