5-Chloro­benzothia­zole-2-spiro-3′-indolin-2′-one

Akkurt, M.; Karaca, S.; Ermut, G.; Karalı, N.; Büyükgüngör, O.

doi:10.1107/S1600536810001285

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages o399-o400

https://doi.org/10.1107/S1600536810001285

Open

access

5-Chlorobenzothiazole-2-spiro-3′-indolin-2′-one

Mehmet Akkurt,^a ^* Selvi Karaca,^a Görkem Ermut,^b Nilgün Karalı ^b and Orhan Büyükgüngör ^c

^aDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey, ^bDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, stanbul University, 34116 Beyazıt–stanbul, Turkey, and ^cDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 16 December 2009; accepted 11 January 2010; online 20 January 2010)

The title compound, C₁₄H₉ClN₂OS, crystallizes with two unique molecules, A and B, in the asymmetric unit. The five-membered rings of the benzothiazole groups in both molecules adopt an envelope conformation [puckering parameters: q₂ = 0.242 (1) Å and φ₂ = 217.5 (4)° for A, and q₂ = 0.234 (1) Å and φ₂ = 37.7 (4)° for B]. The five-membered rings of the indolinone groups in both molecules are also not planar, with a twisted conformation [puckering parameters are q₂ = 0.112 (2) Å and φ₂ = 126.3 (8)° for A, and q₂ = 0.108 (2) Å and φ₂ = 306.4 (9)° for B]. In the crystal structure, there are intermolecular N—H⋯O, N—H⋯S and C—H⋯O hydrogen-bonding interactions, forming the layers propagating normal to c.

Related literature

For general background to and applications of 1H-indole-2,3-dione derivatives, see: Alam & Nawwar (2002 ); Cho et al. (2008 ); Da-Silva et al. (2001 ); Dandia et al. (1990 ); Hall et al. (2009 ); Joshi et al. (1990 ); Kumar et al. (2008 ); Quenelle et al. (2006 ); Vine et al. (2007 , 2009 ); Ćaleta et al. (2009 ). For bond-length data, see: Allen et al. (1987 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₄H₉ClN₂OS
M_r = 288.75
Monoclinic, P 2₁ /c
a = 12.8421 (6) Å
b = 9.1159 (3) Å
c = 22.1553 (9) Å
β = 97.051 (3)°
V = 2574.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 295 K
0.77 × 0.49 × 0.19 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.723, T_max = 0.919
23976 measured reflections
5271 independent reflections
3987 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.080
S = 1.01
5271 reflections
359 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.90 (3)	1.95 (3)	2.840 (2)	171 (2)
N2—H2A⋯S1ⁱⁱ	0.90 (2)	2.61 (2)	3.506 (1)	177 (2)
N3—H3A⋯O1ⁱⁱⁱ	0.89 (2)	1.99 (2)	2.867 (2)	166 (2)
N4—H4A⋯S2^iv	0.89 (2)	2.63 (2)	3.511 (1)	176 (2)
C3—H3⋯O1^v	0.93	2.53	3.418 (2)	161
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810001285/im2170sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001285/im2170Isup2.hkl

checkCIF report

Comment top

1H-Indole-2,3-dione is a synthetically versatile molecule which has led to an array of derivatives displaying a broad spectrum of biological properties including anticancer, antiviral, antituberculosis and antibacterial activities (Vine et al., 2007, 2009; Quenelle et al., 2006). Investigation of the structure-activity relationships in 2-indolinones revealed that cyclization to thiazolines and spiroindolinones are associated with increased activity against a range of human cancer cell lines, various bacteria and viruses (Hall et al., 2009; Kumar et al., 2008). A large number of 2-arylbenzothiazoles have been prepared because of their wide pharmacological potential. This important class of compounds has significant anticancer and antimicrobial properties (Ćaleta et al.,2009; Cho et al., 2008). The reactivity of 1H-indole-2,3-dione towards 2-aminothiophenol has been the subject of a number of reports and some of the products obtained are quite interesting. The first results reported that 1H-indole-2,3-dione furnished benzothiazinone, indolobenzothiazide and spiro benzothiazole when the reaction was carried out in dry xylene in the presence of anhydrous zinc chloride under reflux. On the other hand, the reaction of 1-methyl-1H-indole-2,3-dione with 2-amino thiophenol under the same conditions furnished solely the spiro compound (Joshi et al., 1990; Dandia et al., 1990; Da-Silva et al., 2001). In addition, there is one report on the reaction of 1H-indole-2,3-dione with 2-aminothiophenol in ethanol yielding a single spirobenzothiazole (Alam & Nawwar, 2002). Promoted by the above observations and in continuation of our study on the indolinone derivatives, we synthesized the title compound (3) by incorporating the benzothiazole moiety. Thus spectroscopic and X-ray diffraction studies were carried out on (3) to determine the spiro benzothiazole structure.

Fig. 1 shows the two crystallographically independent molecules in the asymmetric unit. Bond lengths in both molecules are within normal ranges (Allen et al., 1987). The five-membered rings S1/N2/C8/C9/C14 and S2/N4/C22/C23/C28 of the benzothiazole groups in both molecules A and B [A: S1/Cl1/O1/N1/N2/C1–C14 and B: S2/Cl2/O2/N3/N4/C15–C28] adopt an envelope conformation with atom C8 at the flap for molecule A [puckering parameters are q₂ = 0.242 (1) Å and φ₂= 217.5 (4)° (Cremer & Pople, 1975)] and with atom C22 at the flap for molecule B [puckering parameters are q₂ = 0.234 (1) Å and φ₂= 37.7 (4)°]. The five-membered rings N1/C1/C2/C7/C8 and N3/C15/C20—C22 of the indolinone groups in both molecules A and B also are not planar, with twisted C7—C8 and C21—C22 bonds, respectively, [puckering parameters are q₂ = 0.112 (2) Å and φ₂ = 126.3 (8)° for A, and q₂ = 0.108 (2) Å and φ₂ = 306.4 (9)° for B]..

The torsion angles N1—C7—C8—N2, C2–C8–N2–C14 in A and N3—C21—C22—N4, C20—C22—N4—C28 in B are 141.0 (1)°, 148.5 (1)° and -140.3 (1) °, -147.8 (1)°, respectivley. Thus, they adopt +anti-clinal (+ac) and -anti-clinal (-ac) conformations, for molecules A and B, repectively.

The crystal packing is stabilized by intermolecular N—H···O, N—H···S and C—H···O hydrogen bonding interactions, forming the layers of molecules which are paralel to the (001) planes (Table 1 and Fig. 2).

Related literature top

For general background to and applications of 1H-indole-2,3-dione derivatives, see: Alam & Nawwar (2002); Cho et al. (2008); Da-Silva et al. (2001); Dandia et al. (1990); Hall et al. (2009); Joshi et al. (1990); Kumar et al. (2008); Quenelle et al. (2006); Vine et al. (2007, 2009); Ćaleta et al. (2009). For bond-length data, see: Allen et al. (1987). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

To a solution of 1H-indole-2,3-dione 1 (3.5 mmol) in absolute ethanol (15 ml) was added 2-aminothiophenol 2 (3.5 mmol). The mixture was heated under reflux for 5 h. The solid thus obtained (3) was filtered, dried and recrystallized from ethanol (Alam & Nawwar, 2002). Yield: 86%; m.p.: 514 K; IR (KBr) ν (cm^-1): 3281, 3149 (N—H), 1728(C=O); ¹H-NMR (DMSO-d₆, 500 MHz) δ (p.p.m.): 6.50 (1H, d, J = 0.96 Hz, C₁₃—H), 6.62 (1H, dd, J = 8.30, 2.44 Hz, C₁₁—H), 6.84 (1H, d, J = 7.81 Hz, C₆—H), 7.03 (1H, d, J = 8.30 Hz, C₁₀—H), 7.05 (1H, dt, J =7.81 Hz, C₄—H), 7.29 (1H, dt, J = 7.81 Hz, C₅—H), 7.55 (1H, d, J = 2.92 Hz, C₃—H), 7.56 (1H, s, N₂—H), 10.39 (1H, s, N₁—H); ¹³C-NMR (HSQC) (125 MHz)(DMSO-d₆/TMS) δ (p.p.m.): 75.64 (C₈), 108.40 (C₁₃), 118.52 (C₁₁), 110.88 (C₆), 122.70 (C₁₀), 123.28 (C₄), 123.99 (C₂), 126.38 (C₃), 129.86(C₉), 130.92 (C₁₂), 131.43 (C₅), 142.03 (C₁), 149.43 (C₁₄), 176.53 (C₇). MS (ESI+) m/z (%): 289 (MH⁺, 35), 287 (100). Analysis calculated for C₁₄H₉ClN₂OS: C 58.23, H 3.14, N 9.70%. Found: C 58.06, H 3.14, N 9.52%.

Structure description top

For general background to and applications of 1H-indole-2,3-dione derivatives, see: Alam & Nawwar (2002); Cho et al. (2008); Da-Silva et al. (2001); Dandia et al. (1990); Hall et al. (2009); Joshi et al. (1990); Kumar et al. (2008); Quenelle et al. (2006); Vine et al. (2007, 2009); Ćaleta et al. (2009). For bond-length data, see: Allen et al. (1987). For puckering parameters, see: Cremer & Pople (1975).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The title compound (3), with the atom-numbering scheme, intramolecular H-bonds and 50% probability displacement ellipsoids.
	Fig. 2. The packing and hydrogen bonding of the title compound (3) down the b axis. H atoms not involved in hydrogen bonding have been omitted.

5-Chlorobenzothiazole-2-spiro-3'-indolin-2'-one top

Crystal data top

C₁₄H₉ClN₂OS	F(000) = 1184
M_r = 288.75	D_x = 1.490 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 33214 reflections
a = 12.8421 (6) Å	θ = 1.6–28.0°
b = 9.1159 (3) Å	µ = 0.45 mm⁻¹
c = 22.1553 (9) Å	T = 295 K
β = 97.051 (3)°	Prism, yellow
V = 2574.1 (2) Å³	0.77 × 0.49 × 0.19 mm
Z = 8

Data collection top

Stoe IPDS 2 diffractometer	5271 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3987 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.031
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.5°, θ_min = 1.9°
ω scans	h = −14→16
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
T_min = 0.723, T_max = 0.919	l = −27→27
23976 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0445P)² + 0.0864P] where P = (F_o² + 2F_c²)/3
5271 reflections	(Δ/σ)_max < 0.001
359 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₉ClN₂OS	V = 2574.1 (2) Å³
M_r = 288.75	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8421 (6) Å	µ = 0.45 mm⁻¹
b = 9.1159 (3) Å	T = 295 K
c = 22.1553 (9) Å	0.77 × 0.49 × 0.19 mm
β = 97.051 (3)°

Data collection top

Stoe IPDS 2 diffractometer	5271 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	3987 reflections with I > 2σ(I)
T_min = 0.723, T_max = 0.919	R_int = 0.031
23976 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.17 e Å⁻³
5271 reflections	Δρ_min = −0.19 e Å⁻³
359 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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.

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

	x	y	z	U_iso*/U_eq
Cl1	−0.21534 (5)	0.20753 (8)	0.44750 (3)	0.0897 (3)
S1	0.14151 (3)	0.34132 (4)	0.29015 (2)	0.0398 (1)
O1	0.15538 (9)	−0.02243 (11)	0.29802 (5)	0.0468 (4)
N1	0.20968 (12)	0.04018 (14)	0.20602 (7)	0.0459 (5)
N2	−0.02266 (11)	0.17509 (14)	0.25719 (6)	0.0386 (4)
C1	0.17319 (13)	0.13376 (17)	0.15826 (7)	0.0439 (5)
C2	0.09339 (13)	0.22368 (16)	0.17481 (7)	0.0407 (5)
C3	0.04229 (16)	0.32123 (18)	0.13402 (8)	0.0528 (6)
C4	0.0736 (2)	0.3287 (2)	0.07608 (9)	0.0684 (8)
C5	0.1542 (2)	0.2413 (2)	0.06049 (9)	0.0682 (8)
C6	0.20529 (17)	0.1426 (2)	0.10113 (9)	0.0581 (7)
C7	0.15275 (12)	0.05484 (15)	0.25322 (7)	0.0384 (5)
C8	0.08181 (12)	0.19188 (15)	0.24007 (7)	0.0371 (4)
C9	0.04814 (13)	0.31467 (15)	0.34106 (7)	0.0400 (5)
C10	0.04669 (15)	0.3771 (2)	0.39753 (8)	0.0538 (6)
C11	−0.03608 (18)	0.3447 (2)	0.43046 (9)	0.0603 (7)
C12	−0.11329 (15)	0.2499 (2)	0.40578 (8)	0.0541 (6)
C13	−0.11335 (13)	0.18672 (17)	0.34914 (8)	0.0446 (5)
C14	−0.03182 (12)	0.22070 (15)	0.31617 (7)	0.0366 (4)
Cl2	0.71172 (5)	0.55718 (7)	0.05591 (3)	0.0844 (2)
S2	0.35504 (3)	0.42746 (4)	0.21381 (2)	0.0400 (1)
O2	0.34292 (10)	0.79114 (12)	0.20783 (5)	0.0470 (4)
N3	0.29057 (12)	0.72689 (14)	0.30029 (7)	0.0456 (4)
N4	0.52018 (11)	0.59219 (14)	0.24673 (6)	0.0388 (4)
C15	0.32736 (13)	0.63104 (16)	0.34761 (8)	0.0441 (5)
C16	0.29684 (17)	0.6217 (2)	0.40483 (9)	0.0589 (7)
C17	0.3485 (2)	0.5204 (2)	0.44442 (9)	0.0689 (8)
C18	0.4273 (2)	0.4313 (2)	0.42740 (9)	0.0665 (8)
C19	0.45735 (15)	0.44084 (18)	0.36933 (8)	0.0505 (6)
C20	0.40570 (13)	0.54115 (16)	0.32944 (7)	0.0406 (5)
C21	0.34576 (12)	0.71277 (15)	0.25252 (7)	0.0381 (5)
C22	0.41620 (12)	0.57500 (14)	0.26426 (7)	0.0363 (4)
C23	0.44832 (13)	0.45380 (15)	0.16277 (7)	0.0405 (5)
C24	0.44918 (16)	0.3916 (2)	0.10620 (8)	0.0535 (6)
C25	0.53209 (18)	0.4225 (2)	0.07331 (9)	0.0616 (7)
C26	0.60934 (15)	0.5167 (2)	0.09761 (8)	0.0535 (6)
C27	0.60988 (13)	0.58121 (17)	0.15439 (8)	0.0443 (5)
C28	0.52871 (12)	0.54685 (15)	0.18761 (7)	0.0368 (4)
H1A	0.257 (2)	−0.032 (3)	0.2053 (10)	0.081 (7)*
H2A	−0.0558 (16)	0.091 (2)	0.2451 (8)	0.056 (5)*
H3	−0.01150	0.38030	0.14480	0.0630*
H4	0.04000	0.39320	0.04750	0.0820*
H5	0.17450	0.24920	0.02170	0.0820*
H6	0.25940	0.08410	0.09040	0.0700*
H10	0.10020	0.43990	0.41350	0.0650*
H11	−0.03920	0.38640	0.46850	0.0720*
H13	−0.16670	0.12320	0.33360	0.0530*
H3A	0.2402 (19)	0.794 (2)	0.3016 (9)	0.070 (6)*
H4A	0.5540 (16)	0.674 (2)	0.2583 (8)	0.050 (5)*
H16	0.24380	0.68090	0.41650	0.0710*
H17	0.32980	0.51190	0.48350	0.0830*
H18	0.46040	0.36450	0.45510	0.0800*
H19	0.51040	0.38170	0.35770	0.0610*
H24	0.39510	0.32980	0.09020	0.0640*
H25	0.53510	0.37990	0.03540	0.0740*
H27	0.66300	0.64540	0.16960	0.0530*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0863 (5)	0.1113 (5)	0.0817 (4)	−0.0106 (4)	0.0518 (4)	0.0006 (3)
S1	0.0346 (2)	0.0328 (2)	0.0528 (2)	−0.0029 (2)	0.0087 (2)	−0.0030 (2)
O1	0.0451 (7)	0.0386 (5)	0.0585 (7)	0.0065 (5)	0.0138 (6)	0.0070 (5)
N1	0.0440 (8)	0.0377 (7)	0.0591 (9)	0.0076 (6)	0.0185 (7)	−0.0010 (6)
N2	0.0303 (7)	0.0369 (6)	0.0492 (8)	−0.0010 (5)	0.0073 (6)	−0.0045 (6)
C1	0.0438 (9)	0.0372 (7)	0.0527 (9)	−0.0045 (7)	0.0143 (7)	−0.0059 (7)
C2	0.0425 (9)	0.0345 (7)	0.0462 (9)	−0.0026 (6)	0.0095 (7)	−0.0031 (6)
C3	0.0586 (12)	0.0463 (9)	0.0536 (10)	0.0033 (8)	0.0075 (9)	0.0017 (7)
C4	0.0886 (18)	0.0634 (12)	0.0530 (11)	−0.0042 (11)	0.0074 (11)	0.0111 (9)
C5	0.0888 (17)	0.0686 (12)	0.0511 (11)	−0.0163 (12)	0.0241 (11)	−0.0036 (9)
C6	0.0643 (13)	0.0544 (10)	0.0604 (11)	−0.0060 (9)	0.0272 (10)	−0.0081 (9)
C7	0.0326 (8)	0.0307 (7)	0.0530 (9)	−0.0008 (6)	0.0092 (7)	−0.0022 (6)
C8	0.0336 (8)	0.0315 (7)	0.0468 (8)	0.0016 (6)	0.0080 (7)	−0.0016 (6)
C9	0.0371 (9)	0.0345 (7)	0.0487 (9)	0.0003 (6)	0.0060 (7)	0.0005 (6)
C10	0.0572 (12)	0.0538 (9)	0.0505 (10)	−0.0064 (9)	0.0072 (8)	−0.0098 (8)
C11	0.0680 (14)	0.0663 (12)	0.0488 (10)	0.0010 (10)	0.0163 (9)	−0.0085 (9)
C12	0.0537 (12)	0.0582 (10)	0.0543 (10)	0.0052 (9)	0.0225 (9)	0.0079 (8)
C13	0.0369 (9)	0.0421 (8)	0.0561 (10)	0.0020 (7)	0.0109 (8)	0.0049 (7)
C14	0.0320 (8)	0.0329 (7)	0.0453 (8)	0.0044 (6)	0.0063 (6)	0.0016 (6)
Cl2	0.0786 (4)	0.1071 (4)	0.0763 (4)	−0.0002 (3)	0.0450 (3)	0.0068 (3)
S2	0.0353 (2)	0.0323 (2)	0.0531 (2)	−0.0031 (2)	0.0084 (2)	−0.0037 (2)
O2	0.0452 (7)	0.0385 (6)	0.0590 (7)	0.0070 (5)	0.0134 (6)	0.0055 (5)
N3	0.0422 (8)	0.0373 (6)	0.0605 (9)	0.0076 (6)	0.0194 (7)	−0.0010 (6)
N4	0.0308 (7)	0.0364 (6)	0.0499 (8)	−0.0023 (5)	0.0081 (6)	−0.0070 (6)
C15	0.0448 (10)	0.0357 (7)	0.0535 (9)	−0.0046 (7)	0.0133 (7)	−0.0041 (7)
C16	0.0678 (13)	0.0531 (10)	0.0604 (11)	−0.0056 (9)	0.0269 (10)	−0.0083 (9)
C17	0.0906 (17)	0.0673 (12)	0.0523 (11)	−0.0088 (12)	0.0234 (11)	0.0001 (9)
C18	0.0848 (17)	0.0620 (11)	0.0517 (11)	0.0016 (11)	0.0048 (10)	0.0102 (9)
C19	0.0544 (11)	0.0429 (8)	0.0534 (10)	0.0025 (7)	0.0037 (8)	0.0004 (7)
C20	0.0404 (9)	0.0350 (7)	0.0470 (9)	−0.0031 (6)	0.0084 (7)	−0.0042 (6)
C21	0.0313 (8)	0.0311 (7)	0.0526 (9)	−0.0008 (6)	0.0080 (7)	−0.0029 (6)
C22	0.0319 (8)	0.0294 (7)	0.0481 (8)	0.0012 (6)	0.0069 (7)	−0.0025 (6)
C23	0.0382 (9)	0.0343 (7)	0.0495 (9)	0.0023 (6)	0.0075 (7)	−0.0002 (6)
C24	0.0593 (12)	0.0509 (9)	0.0502 (9)	−0.0062 (8)	0.0062 (8)	−0.0075 (8)
C25	0.0736 (15)	0.0652 (12)	0.0482 (10)	0.0052 (10)	0.0169 (10)	−0.0062 (9)
C26	0.0538 (11)	0.0563 (10)	0.0538 (10)	0.0076 (8)	0.0204 (9)	0.0078 (8)
C27	0.0360 (9)	0.0429 (8)	0.0551 (10)	0.0027 (7)	0.0102 (7)	0.0051 (7)
C28	0.0324 (8)	0.0312 (7)	0.0469 (8)	0.0044 (6)	0.0054 (6)	0.0013 (6)

Geometric parameters (Å, º) top

Cl1—C12	1.737 (2)	C11—C12	1.377 (3)
Cl2—C26	1.737 (2)	C12—C13	1.381 (2)
S1—C9	1.7609 (17)	C13—C14	1.383 (2)
S1—C8	1.8617 (15)	C3—H3	0.9300
S2—C22	1.8600 (15)	C4—H4	0.9300
S2—C23	1.7619 (17)	C5—H5	0.9300
O1—C7	1.2142 (18)	C6—H6	0.9300
O2—C21	1.2179 (18)	C10—H10	0.9300
N1—C7	1.354 (2)	C11—H11	0.9300
N1—C1	1.395 (2)	C13—H13	0.9300
N2—C14	1.390 (2)	C15—C16	1.375 (3)
N2—C8	1.446 (2)	C15—C20	1.395 (2)
N1—H1A	0.90 (3)	C16—C17	1.385 (3)
N2—H2A	0.901 (19)	C17—C18	1.386 (3)
N3—C15	1.402 (2)	C18—C19	1.391 (3)
N3—C21	1.350 (2)	C19—C20	1.383 (2)
N4—C28	1.391 (2)	C20—C22	1.499 (2)
N4—C22	1.444 (2)	C21—C22	1.551 (2)
N3—H3A	0.89 (2)	C23—C28	1.396 (2)
N4—H4A	0.885 (19)	C23—C24	1.377 (2)
C1—C2	1.396 (2)	C24—C25	1.391 (3)
C1—C6	1.381 (3)	C25—C26	1.371 (3)
C2—C8	1.500 (2)	C26—C27	1.388 (2)
C2—C3	1.376 (2)	C27—C28	1.384 (2)
C3—C4	1.393 (3)	C16—H16	0.9300
C4—C5	1.383 (3)	C17—H17	0.9300
C5—C6	1.381 (3)	C18—H18	0.9300
C7—C8	1.553 (2)	C19—H19	0.9300
C9—C14	1.398 (2)	C24—H24	0.9300
C9—C10	1.377 (2)	C25—H25	0.9300
C10—C11	1.393 (3)	C27—H27	0.9300

Cl1···Cl2ⁱ	3.6085 (10)	C13···O2^vii	3.206 (2)
Cl2···Cl1ⁱⁱ	3.6085 (10)	C13···C21^vii	3.520 (2)
Cl2···H5ⁱⁱⁱ	2.9700	C13···C3^vii	3.463 (2)
S1···O1	3.3241 (11)	C14···O1	3.3303 (18)
S1···N1	3.4896 (14)	C15···S1	3.6805 (16)
S1···N2^iv	3.5063 (14)	C15···C25^ix	3.551 (3)
S1···C15	3.6805 (16)	C16···C25^ix	3.510 (3)
S1···S2	3.4836 (6)	C19···C27^v	3.414 (2)
S2···N4^v	3.5113 (14)	C21···C13^iv	3.520 (2)
S2···S1	3.4836 (6)	C25···C16^v	3.510 (3)
S2···O2	3.3208 (12)	C25···C15^v	3.551 (3)
S2···N3	3.4923 (14)	C25···C25ⁱⁱⁱ	3.546 (3)
S2···C1	3.6649 (16)	C27···C19^ix	3.414 (2)
S1···H2A^iv	2.606 (19)	C27···C7^ix	3.465 (2)
S1···H27^v	3.1200	C27···O1^ix	3.211 (2)
S2···H13^iv	3.0800	C28···O2	3.3339 (19)
S2···H4A^v	2.628 (19)	C6···H24	3.0100
O1···N2	2.9632 (18)	C7···H3A^vi	2.787 (19)
O1···N3^vi	2.8666 (18)	C7···H27^v	2.8700
O1···S1	3.3241 (11)	C16···H10	3.0500
O1···C3^vii	3.418 (2)	C21···H1A^viii	2.74 (3)
O1···C14	3.3303 (18)	C21···H13^iv	2.9200
O1···C27^v	3.211 (2)	C23···H4A^v	3.095 (18)
O2···C28	3.3339 (19)	C25···H25ⁱⁱⁱ	3.0500
O2···N1^viii	2.8402 (18)	H1A···C21^vi	2.74 (3)
O2···N4	2.9550 (18)	H1A···O2^vi	1.95 (3)
O2···S2	3.3208 (12)	H2A···S1^vii	2.606 (19)
O2···C13^iv	3.206 (2)	H2A···H13	2.5800
O1···H3A^vi	1.99 (2)	H3···O1^iv	2.5300
O1···H27^v	2.8100	H3A···C7^viii	2.787 (19)
O1···H3^vii	2.5300	H3A···O1^viii	1.99 (2)
O2···H1A^viii	1.95 (3)	H4A···S2^ix	2.628 (19)
O2···H13^iv	2.7900	H4A···C23^ix	3.095 (18)
O2···H19^ix	2.6500	H4A···H27	2.5600
N1···S1	3.4896 (14)	H5···Cl2ⁱⁱⁱ	2.9700
N1···O2^vi	2.8402 (18)	H10···C16	3.0500
N2···S1^vii	3.5063 (14)	H13···O2^vii	2.7900
N2···O1	2.9632 (18)	H13···C21^vii	2.9200
N3···O1^viii	2.8666 (18)	H13···S2^vii	3.0800
N3···S2	3.4923 (14)	H13···H2A	2.5800
N4···O2	2.9550 (18)	H19···O2^v	2.6500
N4···S2^ix	3.5113 (14)	H24···C6	3.0100
C1···S2	3.6649 (16)	H25···C25ⁱⁱⁱ	3.0500
C3···C13^iv	3.463 (2)	H27···H4A	2.5600
C3···O1^iv	3.418 (2)	H27···S1^ix	3.1200
C6···C11^vii	3.495 (3)	H27···O1^ix	2.8100
C7···C27^v	3.465 (2)	H27···C7^ix	2.8700
C11···C6^iv	3.495 (3)

C8—S1—C9	91.02 (7)	C5—C6—H6	121.00
C22—S2—C23	90.97 (7)	C9—C10—H10	121.00
C1—N1—C7	111.26 (14)	C11—C10—H10	120.00
C8—N2—C14	113.78 (13)	C10—C11—H11	121.00
C7—N1—H1A	121.2 (15)	C12—C11—H11	120.00
C1—N1—H1A	126.9 (14)	C12—C13—H13	121.00
C8—N2—H2A	115.6 (13)	C14—C13—H13	121.00
C14—N2—H2A	116.3 (12)	C16—C15—C20	121.82 (16)
C15—N3—C21	111.45 (14)	N3—C15—C16	128.34 (16)
C22—N4—C28	113.79 (13)	N3—C15—C20	109.83 (15)
C21—N3—H3A	122.9 (13)	C15—C16—C17	117.16 (19)
C15—N3—H3A	125.6 (13)	C16—C17—C18	121.83 (19)
C28—N4—H4A	115.5 (12)	C17—C18—C19	120.67 (18)
C22—N4—H4A	116.8 (13)	C18—C19—C20	117.82 (17)
N1—C1—C2	110.43 (14)	C15—C20—C19	120.69 (15)
N1—C1—C6	128.38 (16)	C15—C20—C22	108.09 (13)
C2—C1—C6	121.19 (15)	C19—C20—C22	131.22 (15)
C3—C2—C8	131.49 (15)	O2—C21—N3	127.96 (14)
C1—C2—C8	107.61 (13)	O2—C21—C22	124.75 (14)
C1—C2—C3	120.89 (15)	N3—C21—C22	107.29 (12)
C2—C3—C4	117.94 (18)	S2—C22—C20	110.41 (10)
C3—C4—C5	120.76 (18)	S2—C22—C21	106.87 (10)
C4—C5—C6	121.53 (19)	S2—C22—N4	104.66 (10)
C1—C6—C5	117.68 (19)	C20—C22—C21	102.05 (12)
O1—C7—C8	125.24 (14)	N4—C22—C20	118.49 (13)
O1—C7—N1	127.63 (14)	N4—C22—C21	113.99 (12)
N1—C7—C8	107.13 (12)	S2—C23—C28	110.98 (11)
S1—C8—C2	110.54 (10)	C24—C23—C28	121.39 (16)
N2—C8—C2	118.57 (13)	S2—C23—C24	127.60 (13)
N2—C8—C7	114.05 (12)	C23—C24—C25	119.06 (17)
S1—C8—N2	104.39 (10)	C24—C25—C26	118.99 (18)
C2—C8—C7	102.19 (12)	Cl2—C26—C25	118.86 (15)
S1—C8—C7	106.72 (10)	Cl2—C26—C27	118.18 (14)
S1—C9—C14	110.91 (11)	C25—C26—C27	122.96 (18)
C10—C9—C14	121.38 (16)	C26—C27—C28	117.77 (15)
S1—C9—C10	127.68 (13)	N4—C28—C27	125.83 (14)
C9—C10—C11	119.00 (17)	C23—C28—C27	119.79 (14)
C10—C11—C12	118.93 (18)	N4—C28—C23	114.33 (14)
C11—C12—C13	122.87 (18)	C15—C16—H16	121.00
Cl1—C12—C11	118.80 (15)	C17—C16—H16	121.00
Cl1—C12—C13	118.33 (14)	C16—C17—H17	119.00
C12—C13—C14	118.07 (15)	C18—C17—H17	119.00
N2—C14—C13	125.90 (14)	C17—C18—H18	120.00
C9—C14—C13	119.73 (14)	C19—C18—H18	120.00
N2—C14—C9	114.29 (14)	C18—C19—H19	121.00
C4—C3—H3	121.00	C20—C19—H19	121.00
C2—C3—H3	121.00	C23—C24—H24	120.00
C3—C4—H4	120.00	C25—C24—H24	120.00
C5—C4—H4	120.00	C24—C25—H25	121.00
C6—C5—H5	119.00	C26—C25—H25	121.00
C4—C5—H5	119.00	C26—C27—H27	121.00
C1—C6—H6	121.00	C28—C27—H27	121.00

C9—S1—C8—C7	−101.67 (11)	O1—C7—C8—S1	75.43 (17)
C8—S1—C9—C10	171.57 (16)	C10—C9—C14—N2	175.71 (15)
C8—S1—C9—C14	−10.32 (12)	C14—C9—C10—C11	0.4 (3)
C9—S1—C8—N2	19.41 (10)	C10—C9—C14—C13	−1.3 (2)
C9—S1—C8—C2	147.97 (11)	S1—C9—C14—C13	−179.58 (12)
C23—S2—C22—C21	102.41 (11)	S1—C9—C10—C11	178.36 (14)
C23—S2—C22—C20	−147.38 (11)	S1—C9—C14—N2	−2.55 (16)
C22—S2—C23—C28	9.92 (12)	C9—C10—C11—C12	0.7 (3)
C23—S2—C22—N4	−18.82 (10)	C10—C11—C12—Cl1	179.01 (15)
C22—S2—C23—C24	−172.01 (16)	C10—C11—C12—C13	−1.0 (3)
C1—N1—C7—O1	169.93 (15)	C11—C12—C13—C14	0.1 (3)
C1—N1—C7—C8	−10.37 (17)	Cl1—C12—C13—C14	−179.91 (13)
C7—N1—C1—C6	−174.55 (17)	C12—C13—C14—C9	1.0 (2)
C7—N1—C1—C2	4.51 (19)	C12—C13—C14—N2	−175.62 (15)
C8—N2—C14—C9	19.25 (18)	C16—C15—C20—C19	−1.5 (3)
C8—N2—C14—C13	−163.92 (14)	C16—C15—C20—C22	177.60 (16)
C14—N2—C8—S1	−25.03 (14)	N3—C15—C20—C19	177.41 (15)
C14—N2—C8—C2	−148.54 (13)	N3—C15—C20—C22	−3.54 (18)
C14—N2—C8—C7	91.06 (15)	C20—C15—C16—C17	1.0 (3)
C15—N3—C21—C22	10.02 (17)	N3—C15—C16—C17	−177.60 (18)
C21—N3—C15—C16	174.40 (17)	C15—C16—C17—C18	−0.3 (3)
C15—N3—C21—O2	−169.98 (16)	C16—C17—C18—C19	0.0 (3)
C21—N3—C15—C20	−4.37 (19)	C17—C18—C19—C20	−0.3 (3)
C22—N4—C28—C23	−18.74 (18)	C18—C19—C20—C15	1.1 (3)
C28—N4—C22—C20	147.82 (13)	C18—C19—C20—C22	−177.75 (17)
C22—N4—C28—C27	164.02 (14)	C15—C20—C22—S2	−104.54 (13)
C28—N4—C22—C21	−92.09 (15)	C15—C20—C22—C21	8.79 (16)
C28—N4—C22—S2	24.31 (14)	C19—C20—C22—S2	74.4 (2)
N1—C1—C6—C5	177.63 (18)	C15—C20—C22—N4	134.86 (14)
N1—C1—C2—C3	−177.35 (15)	C19—C20—C22—N4	−46.2 (2)
C2—C1—C6—C5	−1.3 (3)	C19—C20—C22—C21	−172.30 (17)
C6—C1—C2—C8	−177.18 (16)	O2—C21—C22—C20	168.65 (15)
N1—C1—C2—C8	3.69 (18)	O2—C21—C22—N4	39.7 (2)
C6—C1—C2—C3	1.8 (3)	N3—C21—C22—C20	−11.35 (16)
C1—C2—C8—S1	104.15 (13)	N3—C21—C22—S2	104.59 (12)
C3—C2—C8—N2	45.7 (2)	N3—C21—C22—N4	−140.30 (13)
C3—C2—C8—C7	172.06 (17)	O2—C21—C22—S2	−75.41 (17)
C1—C2—C8—N2	−135.45 (14)	C28—C23—C24—C25	0.0 (3)
C1—C2—C8—C7	−9.13 (16)	S2—C23—C28—N4	2.57 (16)
C3—C2—C8—S1	−74.7 (2)	C24—C23—C28—N4	−175.64 (15)
C1—C2—C3—C4	−0.8 (3)	C24—C23—C28—C27	1.8 (2)
C8—C2—C3—C4	177.86 (17)	S2—C23—C28—C27	180.00 (12)
C2—C3—C4—C5	−0.5 (3)	S2—C23—C24—C25	−177.89 (14)
C3—C4—C5—C6	0.9 (3)	C23—C24—C25—C26	−1.5 (3)
C4—C5—C6—C1	0.0 (3)	C24—C25—C26—C27	1.2 (3)
N1—C7—C8—C2	11.79 (16)	C24—C25—C26—Cl2	−179.04 (15)
N1—C7—C8—N2	140.99 (13)	Cl2—C26—C27—C28	−179.19 (13)
N1—C7—C8—S1	−104.29 (12)	C25—C26—C27—C28	0.5 (3)
O1—C7—C8—C2	−168.49 (15)	C26—C27—C28—C23	−2.0 (2)
O1—C7—C8—N2	−39.3 (2)	C26—C27—C28—N4	175.09 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^vi	0.90 (3)	1.95 (3)	2.840 (2)	171 (2)
N2—H2A···S1^vii	0.90 (2)	2.61 (2)	3.506 (1)	177 (2)
N3—H3A···O1^viii	0.89 (2)	1.99 (2)	2.867 (2)	166 (2)
N4—H4A···S2^ix	0.89 (2)	2.63 (2)	3.511 (1)	176 (2)
C3—H3···O1^iv	0.93	2.53	3.418 (2)	161

Symmetry codes: (iv) −x, y+1/2, −z+1/2; (vi) x, y−1, z; (vii) −x, y−1/2, −z+1/2; (viii) x, y+1, z; (ix) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉ClN₂OS
M_r	288.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	12.8421 (6), 9.1159 (3), 22.1553 (9)
β (°)	97.051 (3)
V (Å³)	2574.1 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.77 × 0.49 × 0.19

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.723, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	23976, 5271, 3987
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.080, 1.01
No. of reflections	5271
No. of parameters	359
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.90 (3)	1.95 (3)	2.840 (2)	171 (2)
N2—H2A···S1ⁱⁱ	0.90 (2)	2.61 (2)	3.506 (1)	177 (2)
N3—H3A···O1ⁱⁱⁱ	0.89 (2)	1.99 (2)	2.867 (2)	166 (2)
N4—H4A···S2^iv	0.89 (2)	2.63 (2)	3.511 (1)	176 (2)
C3—H3···O1^v	0.93	2.53	3.418 (2)	161.00

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

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

References

Alam, Y. A. & Nawwar, G. A. M. (2002). Heteroat. Chem. 13, 207–210. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ćaleta, I., Kralj, M., Marjanović, M., Bertoša, B., Tomić, S., Pavlović, G., Pavelić, K. & Karminski-Zamola, G. (2009). J. Med. Chem. 52, 1744–1756. Web of Science PubMed Google Scholar
Cho, Y., Loerger, T. R. & Sacchettini, J. C. (2008). J. Med. Chem. 51, 5984–5992. Web of Science CrossRef PubMed CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Dandia, A., Khanna, S. & Joshi, K. C. (1990). J. Indian Chem. Soc. 67, 824–826. CAS Google Scholar
Da-Silva, J. F. M., Garden, S. J. & Pinto, A. C. (2001). J. Braz. Chem. Soc. 12, 273–324. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hall, M. D., Salam, N. K., Hellawell, J. L., Fales, H. M., Kensler, C. B., Ludwig, J. A., Szakács, G., Hibbs, D. E. & Gottesman, M. M. (2009). J. Med. Chem. 52, 3191–3204. Web of Science CrossRef PubMed CAS Google Scholar
Joshi, K. C., Dandia, A. & Khanna, S. (1990). Indian J. Chem. Soc. Sect. B, 29, 824–829. Google Scholar
Kumar, R. R., Perumal, S., Senthilkumar, P., Yogeeswari, P. & Sriram, D. (2008). J. Med. Chem. 51, 5731–5735. Web of Science CSD CrossRef PubMed CAS Google Scholar
Quenelle, D. C., Keith, K. A. & Kern, K. E. R. (2006). Antiviral Res. 71, 24–30. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar
Vine, K. L., Locke, J. M., Ranson, M., Pyne, S. G. & Bremner, J. B. (2007). Bioorg. Med. Chem. 15, 931–938. Web of Science CrossRef PubMed CAS Google Scholar
Vine, K. L., Matesic, L., Locke, J. M., Ranson, M. & Skropeta, D. (2009). Anti-Cancer Agents Med. Chem. 9, 397–414. Web of Science CrossRef PubMed CAS Google Scholar