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

Mehmet Akkurt; Selvi Karaca; Görkem Ermut; Nilgün Karalı; Orhan Büyükgüngör

doi:10.1107/S1600536810001285

. 2010 Jan 20;66(Pt 2):o399–o400. doi: 10.1107/S1600536810001285

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

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

PMCID: PMC2979878 PMID: 21579820

Abstract

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: q ₂ = 0.242 (1) Å and ϕ₂ = 217.5 (4)° for A, and q ₂ = 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 q ₂ = 0.112 (2) Å and ϕ₂ = 126.3 (8)° for A, and q ₂ = 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,
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[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 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

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 ▶).

Supplementary Material

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

e-66-0o399-sup1.cif^{(29.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001285/im2170Isup2.hkl

e-66-0o399-Isup2.hkl^{(252.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

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).

supplementary crystallographic information

Comment

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).

Experimental

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%.