Ethyl 4-(4-chloro­phen­yl)-5-cyano-2-methyl-6-sulfanylidene­-1,6-di­hydropyridine-3-carboxyl­ate

Mague, J.T.; Mohamed, S.K.; Akkurt, M.; Bakhite, E.A.; Albayati, M.R.

doi:10.1107/S2414314616005319

organic compounds

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ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160531

doi:10.1107/S2414314616005319

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Ethyl 4-(4-chlorophenyl)-5-cyano-2-methyl-6-sulfanylidene-1,6-dihydropyridine-3-carboxylate

Joel T. Mague,^a Shaaban K. Mohamed,^b,^c Mehmet Akkurt,^d Etify A. Bakhite ^e and Mustafa R. Albayati ^f ^*

^aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^bChemistry and Environmental Division, Manchester Metropolitan University, Manchester, M1 5GD, England, ^cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^eChemistry Department, Faculty of Science, Assiut University, 71516 Assiut, Egypt, and ^fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 17 March 2016; accepted 29 March 2016; online 5 April 2016)

In the title compound, C₁₆H₁₃ClN₂O₂S, the dihedral angle between the 4-chlorophenyl ring and the pyridine ring is 63.53 (6)°. There is an intramolecular C—H⋯O contact present. In the crystal, molecules are linked by pairs of N—H⋯S hydrogen bonds, forming inversion dimers. The dimers are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming slabs parallel to the ab plane.

Keywords: crystal structure; 3-cyanopyridine; thioxopyridine; hydrogen bonding.

CCDC reference: 1471195

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Chemical scheme

Structure description

Pyridine scaffold compounds continue to attract great interest due to their wide variety of interesting biological activities. They exhibit anticancer, analgesic, antimicrobial and antidepressant activities (Kumar et al., 2011 ). In addition, pyridines are used in the pharmaceutical industry as raw materials for various drugs, vitamins and fungicides (Kumar et al., 2011). These facts promoted us to synthesize and determine the crystal structure of the title compound.

In the title compound, Fig. 1, the pyridine and chlorobenzene rings make a dihedral angle of 63.53 (8)° with each other. The C3—C4—C14—O1, C3—C4—C14—O2, C4—C14—O2—C15 and C14—O2—C15—C16 torsion angles are −133.26 (19), 47.2 (2), 179.63 (13) and 88.8 (2)°, respectively. The conformation of the molecule is partially determined by a weak intramolecular C6—H6A⋯O1 contact (Table 1). In the crystal, pairwise N—H⋯S hydrogen bonds link the molecules to form inversion dimers which further associate via C—H⋯O and C—H⋯N hydrogen bonds, forming slabs parallel to the ab plane (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.91	2.40	3.2911 (14)	166
C6—H6A⋯O1	0.98	2.36	3.047 (2)	127
C6—H6B⋯N2ⁱⁱ	0.98	2.45	3.305 (2)	145
C15—H15B⋯O1ⁱⁱⁱ	0.99	2.41	3.327 (2)	153
Symmetry codes: (i) -x+3, -y+1, -z+1; (ii) x+1, y-1, z; (iii) x-1, y, z.

Figure 1
The molecular structure of the title compound, with atom labelling and 50% probability ellipsoids.

Figure 2
The crystal packing of the title compound projected onto ( $[\overline{1}]$ 10), with the hydrogen bonds shown as blue and black dashed lines (see Table 1

Synthesis and crystallization

To a mixture of 4-chlorobenzylidenecyanothioacetamide (2.22 g, 10 mmol) and ethyl acetoacetate (1.3 ml, 10 mmol) in ethanol (35 ml), three drops of piperidine were added. The resulting mixture was heated under reflux for 3 h and then allowed to stand overnight. The solid that separated was collected and recrystallized from ethanol as orange plates of the title compound (yield: 64%; m.p. 528 K). IR (KBr, cm⁻¹) ν = 3200 (NH), 2220 (C N), 1700 (C=O). ¹H NMR (DMSO-d₆, p.p.m.): δ 13.6 (s, 1H, NH), 7.4–7.8 (dd, 4H, ArH), 3.8–4.1(q, 2H, OCH₂), 2.6 (s, 3H, CH₃ at C-6), 0.8–1.0 (t, 3H, CH₃)

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₃ClN₂O₂S
M_r	332.79
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	5.9498 (2), 8.0999 (2), 16.3919 (4)
α, β, γ (°)	85.990 (1), 81.410 (1), 82.294 (1)
V (Å³)	773.05 (4)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	3.52
Crystal size (mm)	0.25 × 0.20 × 0.03

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.69, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	5834, 2833, 2591
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.05
No. of reflections	2833
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.37
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ), SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1471195

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616005319/su4024sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616005319/su4024Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616005319/su4024Isup3.cml

checkCIF report

Experimental top

To a mixture of 4-chlorobenzylidenecyanothioacetamide (2.22 g, 10 mmol) and ethyl acetoacetate (1.3 ml, 10 mmol) in ethanol (35 ml), three drops of piperidine were added. The resulting mixture was heated under reflux for 3 h and then allowed to stand overnight. The solid that separated was collected and recrystallized from ethanol as orange plates of the title compound (yield: 64%; m.p. 528 K). IR (KBr, cm^-1) ν = 3200 (NH), 2220 (C≡N), 1700 (C═ O). ¹H NMR (DMSO-d₆, p.p.m.): δ 13.6 (s, 1H, NH), 7.4–7.8 (dd, 4H, ArH), 3.8–4.1(q, 2H, OCH₂), 2.6 (s, 3H, CH₃ at C-6), 0.8–1.0 (t, 3H, CH₃)

Structure description top

Pyridine scaffold compounds continue to attract great interest due to their wide variety of interesting biological activities. They exhibit anticancer, analgesic, antimicrobial and antidepressant activities (Kumar et al., 2011). In addition, pyridines are used in the pharmaceutical industry as raw materials for various drugs, vitamins and fungicides (Kumar et al., 2011). These facts promoted us to synthesize and determine the crystal structure of the title compound.

In the title compound, Fig. 1, the pyridine and chlorobenzene rings make a dihedral angle of 63.53 (8)° with each other. The C3—C4—C14—O1, C3—C4—C14—O2, C4—C14—O2—C15 and C14—O2—C15—C16 torsion angles are -133.26 (19), 47.2 (2), 179.63 (13) and 88.8 (2)°, respectively. The conformation of the molecule is partially determined by a weak intramolecular C6—H6A···O1 contact (Table 1). In the crystal, pairwise N—H···S hydrogen bonds link the molecules to form inversion dimers which further associate via C—H···O and C—H···N hydrogen bonds, forming slabs parallel to the ab plane (Fig. 2 and Table 1).

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling and 50% probability ellipsoids.
	Fig. 2. The crystal packing of the title compound projected onto (110), with the hydrogen bonds shown as blue and black dashed lines (see Table 1).

Ethyl 4-(4-chlorophenyl)-5-cyano-2-methyl-6-sulfanylidene-1,6-dihydropyridine-3-carboxylate top

Crystal data top

C₁₆H₁₃ClN₂O₂S	Z = 2
M_r = 332.79	F(000) = 344
Triclinic, P1	D_x = 1.430 Mg m⁻³
a = 5.9498 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 8.0999 (2) Å	Cell parameters from 4687 reflections
c = 16.3919 (4) Å	θ = 2.7–72.1°
α = 85.990 (1)°	µ = 3.52 mm⁻¹
β = 81.410 (1)°	T = 150 K
γ = 82.294 (1)°	Plate, yellow
V = 773.05 (4) Å³	0.25 × 0.20 × 0.03 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2833 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2591 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.1°, θ_min = 2.7°
ω scans	h = −7→6
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −9→9
T_min = 0.69, T_max = 0.90	l = −20→19
5834 measured reflections

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)] = 0.037	Hydrogen site location: mixed
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0667P)² + 0.2083P] where P = (F_o² + 2F_c²)/3
2833 reflections	(Δ/σ)_max = 0.001
201 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₆H₁₃ClN₂O₂S	γ = 82.294 (1)°
M_r = 332.79	V = 773.05 (4) Å³
Triclinic, P1	Z = 2
a = 5.9498 (2) Å	Cu Kα radiation
b = 8.0999 (2) Å	µ = 3.52 mm⁻¹
c = 16.3919 (4) Å	T = 150 K
α = 85.990 (1)°	0.25 × 0.20 × 0.03 mm
β = 81.410 (1)°

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2833 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2016)	2591 reflections with I > 2σ(I)
T_min = 0.69, T_max = 0.90	R_int = 0.027
5834 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	Δρ_max = 0.30 e Å⁻³
2833 reflections	Δρ_min = −0.37 e Å⁻³
201 parameters

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while that attached to nitrogen was placed in a location derived from a difference map and its coordinates adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

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

	x	y	z	U_iso*/U_eq
Cl1	0.09171 (9)	0.76572 (7)	0.95570 (3)	0.04561 (17)
S1	1.25779 (7)	0.71159 (5)	0.50649 (2)	0.02518 (14)
O1	0.9605 (2)	0.10792 (18)	0.79003 (9)	0.0391 (3)
O2	0.6182 (2)	0.21882 (14)	0.75633 (7)	0.0241 (3)
N1	1.2163 (2)	0.41120 (16)	0.58006 (8)	0.0217 (3)
H1	1.3513	0.3821	0.5473	0.032*
N2	0.7694 (3)	0.93321 (19)	0.63377 (11)	0.0366 (4)
C1	1.1310 (3)	0.5763 (2)	0.57500 (10)	0.0211 (3)
C2	0.9336 (3)	0.62163 (19)	0.63293 (10)	0.0210 (3)
C3	0.8416 (3)	0.5079 (2)	0.69179 (10)	0.0210 (3)
C4	0.9405 (3)	0.3390 (2)	0.69120 (10)	0.0216 (3)
C5	1.1289 (3)	0.2924 (2)	0.63341 (10)	0.0225 (3)
C6	1.2464 (3)	0.1199 (2)	0.61975 (12)	0.0283 (4)
H6A	1.1775	0.0420	0.6616	0.042*
H6B	1.4095	0.1163	0.6241	0.042*
H6C	1.2294	0.0881	0.5646	0.042*
C7	0.8412 (3)	0.7947 (2)	0.63293 (10)	0.0242 (4)
C8	0.6520 (3)	0.56935 (19)	0.75689 (10)	0.0215 (3)
C9	0.6899 (3)	0.5590 (2)	0.83914 (10)	0.0257 (4)
H9	0.8330	0.5081	0.8535	0.031*
C10	0.5192 (3)	0.6227 (2)	0.90009 (11)	0.0298 (4)
H10	0.5460	0.6186	0.9559	0.036*
C11	0.3092 (3)	0.6923 (2)	0.87861 (11)	0.0287 (4)
C12	0.2688 (3)	0.7062 (2)	0.79737 (11)	0.0290 (4)
H12	0.1248	0.7565	0.7835	0.035*
C13	0.4419 (3)	0.6454 (2)	0.73635 (10)	0.0251 (4)
H13	0.4170	0.6557	0.6802	0.030*
C14	0.8448 (3)	0.2090 (2)	0.75146 (10)	0.0246 (4)
C15	0.5085 (3)	0.0965 (2)	0.81314 (11)	0.0287 (4)
H15A	0.6140	−0.0088	0.8150	0.034*
H15B	0.3684	0.0724	0.7928	0.034*
C16	0.4470 (5)	0.1599 (3)	0.89807 (13)	0.0514 (6)
H16A	0.3688	0.0777	0.9345	0.077*
H16B	0.3453	0.2653	0.8960	0.077*
H16C	0.5866	0.1781	0.9194	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0386 (3)	0.0553 (3)	0.0385 (3)	−0.0061 (2)	0.0172 (2)	−0.0194 (2)
S1	0.0246 (2)	0.0228 (2)	0.0251 (2)	−0.00264 (15)	0.00473 (17)	0.00094 (15)
O1	0.0257 (7)	0.0429 (8)	0.0452 (8)	−0.0029 (5)	−0.0042 (6)	0.0177 (6)
O2	0.0204 (6)	0.0236 (6)	0.0274 (6)	−0.0048 (4)	0.0009 (5)	−0.0001 (5)
N1	0.0190 (7)	0.0217 (7)	0.0228 (7)	−0.0020 (5)	0.0020 (6)	−0.0028 (5)
N2	0.0318 (9)	0.0269 (8)	0.0459 (10)	0.0004 (6)	0.0076 (7)	−0.0016 (7)
C1	0.0209 (8)	0.0221 (8)	0.0205 (7)	−0.0027 (6)	−0.0026 (6)	−0.0037 (6)
C2	0.0211 (8)	0.0206 (8)	0.0210 (7)	−0.0022 (6)	−0.0013 (6)	−0.0042 (6)
C3	0.0185 (8)	0.0262 (8)	0.0186 (7)	−0.0035 (6)	−0.0020 (6)	−0.0036 (6)
C4	0.0197 (8)	0.0230 (8)	0.0221 (7)	−0.0035 (6)	−0.0019 (6)	−0.0015 (6)
C5	0.0208 (8)	0.0229 (8)	0.0236 (8)	−0.0038 (6)	−0.0015 (7)	−0.0017 (6)
C6	0.0262 (9)	0.0206 (8)	0.0348 (9)	−0.0003 (6)	0.0036 (7)	−0.0008 (7)
C7	0.0218 (9)	0.0247 (9)	0.0241 (8)	−0.0025 (6)	0.0034 (7)	−0.0023 (6)
C8	0.0227 (8)	0.0205 (8)	0.0209 (8)	−0.0055 (6)	0.0015 (6)	−0.0035 (6)
C9	0.0283 (9)	0.0258 (8)	0.0223 (8)	−0.0028 (6)	−0.0016 (7)	−0.0022 (6)
C10	0.0380 (10)	0.0310 (9)	0.0200 (8)	−0.0087 (7)	0.0020 (7)	−0.0036 (7)
C11	0.0293 (10)	0.0279 (9)	0.0268 (8)	−0.0072 (7)	0.0100 (7)	−0.0093 (7)
C12	0.0236 (9)	0.0287 (9)	0.0337 (9)	−0.0031 (6)	0.0010 (7)	−0.0050 (7)
C13	0.0234 (9)	0.0295 (9)	0.0225 (8)	−0.0052 (6)	0.0000 (7)	−0.0044 (6)
C14	0.0225 (9)	0.0245 (8)	0.0257 (8)	−0.0036 (6)	0.0006 (7)	−0.0011 (6)
C15	0.0272 (9)	0.0279 (9)	0.0305 (9)	−0.0113 (7)	0.0037 (7)	0.0007 (7)
C16	0.0672 (16)	0.0527 (13)	0.0337 (11)	−0.0275 (12)	0.0154 (11)	−0.0070 (10)

Geometric parameters (Å, º) top

Cl1—C11	1.7422 (17)	C6—H6B	0.9800
S1—C1	1.6814 (17)	C6—H6C	0.9800
O1—C14	1.204 (2)	C8—C13	1.395 (2)
O2—C14	1.331 (2)	C8—C9	1.395 (2)
O2—C15	1.4620 (19)	C9—C10	1.387 (3)
N1—C5	1.357 (2)	C9—H9	0.9500
N1—C1	1.367 (2)	C10—C11	1.385 (3)
N1—H1	0.9099	C10—H10	0.9500
N2—C7	1.146 (2)	C11—C12	1.383 (3)
C1—C2	1.420 (2)	C12—C13	1.389 (3)
C2—C3	1.390 (2)	C12—H12	0.9500
C2—C7	1.435 (2)	C13—H13	0.9500
C3—C4	1.415 (2)	C15—C16	1.494 (3)
C3—C8	1.491 (2)	C15—H15A	0.9900
C4—C5	1.384 (2)	C15—H15B	0.9900
C4—C14	1.502 (2)	C16—H16A	0.9800
C5—C6	1.492 (2)	C16—H16B	0.9800
C6—H6A	0.9800	C16—H16C	0.9800

C14—O2—C15	115.95 (13)	C10—C9—H9	119.9
C5—N1—C1	126.21 (14)	C8—C9—H9	119.9
C5—N1—H1	118.0	C11—C10—C9	119.25 (16)
C1—N1—H1	115.5	C11—C10—H10	120.4
N1—C1—C2	114.40 (14)	C9—C10—H10	120.4
N1—C1—S1	121.52 (13)	C12—C11—C10	121.55 (17)
C2—C1—S1	124.07 (12)	C12—C11—Cl1	119.24 (15)
C3—C2—C1	122.33 (14)	C10—C11—Cl1	119.20 (14)
C3—C2—C7	120.41 (15)	C11—C12—C13	118.94 (17)
C1—C2—C7	117.08 (14)	C11—C12—H12	120.5
C2—C3—C4	118.89 (14)	C13—C12—H12	120.5
C2—C3—C8	119.03 (14)	C12—C13—C8	120.49 (16)
C4—C3—C8	121.95 (14)	C12—C13—H13	119.8
C5—C4—C3	119.21 (15)	C8—C13—H13	119.8
C5—C4—C14	119.27 (14)	O1—C14—O2	124.50 (16)
C3—C4—C14	121.52 (14)	O1—C14—C4	123.73 (16)
N1—C5—C4	118.84 (15)	O2—C14—C4	111.76 (13)
N1—C5—C6	114.21 (14)	O2—C15—C16	110.94 (14)
C4—C5—C6	126.90 (15)	O2—C15—H15A	109.5
C5—C6—H6A	109.5	C16—C15—H15A	109.5
C5—C6—H6B	109.5	O2—C15—H15B	109.5
H6A—C6—H6B	109.5	C16—C15—H15B	109.5
C5—C6—H6C	109.5	H15A—C15—H15B	108.0
H6A—C6—H6C	109.5	C15—C16—H16A	109.5
H6B—C6—H6C	109.5	C15—C16—H16B	109.5
N2—C7—C2	179.0 (2)	H16A—C16—H16B	109.5
C13—C8—C9	119.50 (16)	C15—C16—H16C	109.5
C13—C8—C3	121.05 (14)	H16A—C16—H16C	109.5
C9—C8—C3	119.35 (15)	H16B—C16—H16C	109.5
C10—C9—C8	120.20 (17)

C5—N1—C1—C2	0.7 (2)	C4—C3—C8—C13	−121.73 (17)
C5—N1—C1—S1	179.31 (12)	C2—C3—C8—C9	−114.02 (17)
N1—C1—C2—C3	2.4 (2)	C4—C3—C8—C9	61.9 (2)
S1—C1—C2—C3	−176.18 (12)	C13—C8—C9—C10	0.5 (2)
N1—C1—C2—C7	177.60 (14)	C3—C8—C9—C10	176.94 (15)
S1—C1—C2—C7	−1.0 (2)	C8—C9—C10—C11	1.8 (3)
C1—C2—C3—C4	−3.5 (2)	C9—C10—C11—C12	−2.7 (3)
C7—C2—C3—C4	−178.47 (14)	C9—C10—C11—Cl1	177.79 (13)
C1—C2—C3—C8	172.56 (14)	C10—C11—C12—C13	1.4 (3)
C7—C2—C3—C8	−2.4 (2)	Cl1—C11—C12—C13	−179.14 (13)
C2—C3—C4—C5	1.4 (2)	C11—C12—C13—C8	0.9 (3)
C8—C3—C4—C5	−174.47 (14)	C9—C8—C13—C12	−1.9 (2)
C2—C3—C4—C14	−178.12 (14)	C3—C8—C13—C12	−178.24 (15)
C8—C3—C4—C14	6.0 (2)	C15—O2—C14—O1	0.1 (2)
C1—N1—C5—C4	−2.6 (2)	C15—O2—C14—C4	179.63 (13)
C1—N1—C5—C6	174.96 (15)	C5—C4—C14—O1	47.2 (2)
C3—C4—C5—N1	1.4 (2)	C3—C4—C14—O1	−133.26 (19)
C14—C4—C5—N1	−179.01 (14)	C5—C4—C14—O2	−132.40 (16)
C3—C4—C5—C6	−175.77 (15)	C3—C4—C14—O2	47.2 (2)
C14—C4—C5—C6	3.8 (3)	C14—O2—C15—C16	88.8 (2)
C2—C3—C8—C13	62.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.91	2.40	3.2911 (14)	166
C6—H6A···O1	0.98	2.36	3.047 (2)	127
C6—H6B···N2ⁱⁱ	0.98	2.45	3.305 (2)	145
C15—H15B···O1ⁱⁱⁱ	0.99	2.41	3.327 (2)	153

Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x+1, y−1, z; (iii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.91	2.40	3.2911 (14)	166
C6—H6A···O1	0.98	2.36	3.047 (2)	127
C6—H6B···N2ⁱⁱ	0.98	2.45	3.305 (2)	145
C15—H15B···O1ⁱⁱⁱ	0.99	2.41	3.327 (2)	153

Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x+1, y−1, z; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃ClN₂O₂S
M_r	332.79
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	5.9498 (2), 8.0999 (2), 16.3919 (4)
α, β, γ (°)	85.990 (1), 81.410 (1), 82.294 (1)
V (Å³)	773.05 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	3.52
Crystal size (mm)	0.25 × 0.20 × 0.03

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.69, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	5834, 2833, 2591
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.05
No. of reflections	2833
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.37

Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a), SHELXL2014/7 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).

Acknowledgements

The support of NSF-MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

Brandenburg, K. & Putz, H. (2012). DIAMOND, Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS, Inc., Madison, WI. Google Scholar
Kumar, S., Sharma, P. K., Dudhe, R. & Kumar, N. (2011). J. Chronother. Drug Deliv. 2, 71–78. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science 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

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