6-Meth­oxy-9-phenyl­sulfonyl-2-(2-thien­yl)-9H-thieno[2,3-b]carbazole

Chakkaravarthi, G.; Marx, A.; Dhayalan, V.; Mohanakrishnan, A.K.; Manivannan, V.

doi:10.1107/S1600536809003493

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages o464-o465

doi:10.1107/S1600536809003493

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6-Methoxy-9-phenylsulfonyl-2-(2-thienyl)-9H-thieno[2,3-b]carbazole

G. Chakkaravarthi,^a ^* A. Marx,^b V. Dhayalan,^c A. K. Mohanakrishnan ^c and V. Manivannan ^b

^aDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^bDepartment of Physics, Presidency College, Chennai 600 005, India, and ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com

(Received 27 January 2009; accepted 28 January 2009; online 6 February 2009)

In the title compound, C₂₅H₁₇NO₃S₃, the mean planes of the thieno[2,3-b]carbazole and phenyl rings are inclined at an angle of 63.6 (1)°. The molecular structure features short intramolecular C—H⋯O contacts and the crystal packing exhibits weak intermolecular C—H⋯S and π–π interactions [centroid-to-centroid distances 3.734 (2)–3.888 (2) Å].

Related literature

For biological activities of carbazole derivatives, see: Diaz et al. (2002 ); Itoigawa et al. (2000 ); Ramsewak et al. (1999 ); Tachibana et al. (2001 ); Zhang et al. (2004 ). For the structures of closely related compounds, see: Chakkaravarthi et al. (2008a ,b ); Hökelek et al. (1998 ). For bond-length data, see: Allen et al. (1987 ). For graph-set notation, see: Etter et al. (1990 ). For general background, see: Govindasamy et al. (1998 ).

Experimental

Crystal data

C₂₅H₁₇NO₃S₃
M_r = 475.58
Orthorhombic, P b c a
a = 15.3900 (12) Å
b = 10.1269 (7) Å
c = 28.233 (2) Å
V = 4400.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 295 (2) K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEX2 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.914, T_max = 0.931
25628 measured reflections
5212 independent reflections
3570 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.175
S = 1.04
5212 reflections
290 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1	0.93	2.57	2.930 (4)	103
C8—H8⋯O1	0.93	2.39	2.940 (3)	117
C19—H19⋯O2	0.93	2.39	2.943 (4)	118
C22—H22⋯S2ⁱ	0.93	2.80	3.684 (3)	158
Symmetry code: (i) -x+2, -y-1, -z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003493/bt2862sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003493/bt2862Isup2.hkl

checkCIF report

Comment top

In continuation of our studies of carbazole derivatives, which are found to possess various biological activities, such as antitumor (Itoigawa et al., 2000), antioxidative (Tachibana et al., 2001), anti-inflammatory and antimutagenic (Ramsewak et al., 1999), the crystal structure of the title compound has been determined. These compounds are thermally and photochemically stable, which makes them useful materials for technological applications. For instance, the carbazole ring is easily functionalized and covalently linked to other molecules (Diaz et al., 2002). This enables its use as a convenient building block for the design and synthesis of molecular glasses, which are widely studied as components of electroactive and photoactive materials (Zhang et al., 2004).

The geometric parameters of the title molecule (Fig. 1) agree well with reported similar structures (Chakkaravarthi et al., 2008a,b; Hökelek et al., 1998). The mean planes of thieno[2,3-b]carbazole and phenyl rings are inclined at an angle of 63.6 (1)°. Thiophene ring C21/C22/C23/C24/S3 forms a dihedral angle of 49.2 (1)° with phenyl ring. The methoxy group is slightly twisted [torsion angle C16—C17—O3—C25 is 13.9 (5)°] out of the plane of the benzene ring C15–C20.

The N—C bond lengths, namely N1—C7 and N1—C20 [1.434 (4) and 1.450 (4) Å] deviate slightly from the normal mean value reported in the literature (Allen et al., 1987). This indicates that the substitution of the phenylsulfonyl group at atom N1 results the lengthening of C—N bond lengths. This may be due to the electron-withdrawing character of the phenylsulfonyl group (Govindasamy et al., 1998).

A distorted tetrahedral geometry around S1 is observed. The deviations being seen for the O—S—O [O1—S1—O2 119.3 (1)°] and O—S—N [O1—S1—N1 106.8 (1)°] angles. The widening of the angles may be due to repulsive interactions between the two short S═O bonds, similar to what is observed in similar structures (Chakkaravarthi et al., 2008a,b). The sum of the bond angles around N1 [343.3 (2)°] indicate the sp² hybridized state of the atom N1 in the molecule.

The torsion angles O1—S1—N1—C7 and O1—S1—C1—C6 [50.2 (2)° and -22.3 (3)°, respectively] describe the syn conformation of the phenylsulfonyl group with respect to carbazole ring system. This conformation is influenced by the intramolecular C—H··· O hydrogen bonds (Table 1); C6—H6··· O1, C8—H8··· O1 and C19—H19···O2, involving sulfonyl atoms O1 and O2. In addition, intramolecular C8—H8···O1 and C19—H19···O2 hydrogen bonds form six-membered rings, both with a graph-set motif of S(6) and C19—H19···O2 forms five-membered ring, with graph-set motif of S(5). The intermolecular C22—H22—S2 interaction generates a ten-membered ring, with graph-set motif of R₂²(10) (Etter et al., 1990).

The crystal structure of the title compound is stabilized by weak intermolecular C—H···S (Fig. 2 and Table 1) and π–π [Cg1···Cg3(2 - x, -y, -z) distance of 3.781 (2) Å; Cg1···Cg5(2 - x, -y, -z) distance of 3.734 (2) Å; Cg2···Cg6(2 - x, -y, -z) distance of 3.888 (2) Å, Cg3···Cg1(2 - x, -y, -z) distance of 3.781 (2) Å, Cg5···Cg5(2 - x, -y, -z) distance of 3.770 (2) Å and Cg6···Cg2(1 - x, 1 - y, -z) distance of 3.888 (2) Å (Cg1, Cg2, Cg3, Cg5 and Cg6 are the centroid of the rings defined by the atoms S2/C9/C12/C11/C10, S3/C21/C22/C23/C24, N1/C7/C14/C15/C20, C7/C8/C9/C12/C13/C14 and C15–C20, respectively)] interactions.

Related literature top

For biological activities of carbazole derivatives, see: Diaz et al. (2002); Itoigawa et al. (2000); Ramsewak et al. (1999); Tachibana et al. (2001); Zhang et al. (2004). For the structures of closely related compounds, see: Chakkaravarthi et al. (2008a,b); Hökelek et al. (1998). For bond-length data, see: Allen et al. (1987). For graph-set notation, see: Etter et al. (1990). For general background, see: Govindasamy et al. (1998).

Experimental top

To a solution of diethyl-2-((2-bromomethyl)-5-methoxy-1- (phenylsulfonyl)-1H-indol-3-yl)methylene)malonate (0.2 g, 0.36 mmol) in dry 1,2-DCE (8 ml), ZnBr₂ (0.16 g, 0.71 mmol) and bithiophene (0.07 g, 0.42 mmol) were added. The reaction mixture was then refluxed for 2 h under N₂ atmosphere. It was then poured over ice–water (50 ml) containing 2 ml of conc. HCl, extracted with chloroform (3 × 10 ml) and dried (Na₂SO₄). The removal of solvent followed by flash column chromatographic purification (silica gel, 230–420 mesh, n-hexane/ethyl acetate 99:1) afforded the compound (I), suitable for X-ray analysis..

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound, viewed down the b axis. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

6-Methoxy-9-phenylsulfonyl-2-(2-thienyl)-9H-thieno[2,3-b]carbazole top

Crystal data top

C₂₅H₁₇NO₃S₃	F(000) = 1968
M_r = 475.58	D_x = 1.436 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6275 reflections
a = 15.3900 (12) Å	θ = 2.5–25.4°
b = 10.1269 (7) Å	µ = 0.37 mm⁻¹
c = 28.233 (2) Å	T = 295 K
V = 4400.2 (6) Å³	Block, colourless
Z = 8	0.25 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEX2 diffractometer	5212 independent reflections
Radiation source: fine-focus sealed tube	3570 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω and ϕ scans	θ_max = 27.8°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→20
T_min = 0.914, T_max = 0.931	k = −7→13
25628 measured reflections	l = −37→36

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0908P)² + 2.7061P] where P = (F_o² + 2F_c²)/3
5212 reflections	(Δ/σ)_max < 0.001
290 parameters	Δρ_max = 0.55 e Å⁻³
2 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₂₅H₁₇NO₃S₃	V = 4400.2 (6) Å³
M_r = 475.58	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.3900 (12) Å	µ = 0.37 mm⁻¹
b = 10.1269 (7) Å	T = 295 K
c = 28.233 (2) Å	0.25 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEX2 diffractometer	5212 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3570 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.931	R_int = 0.040
25628 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	2 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.04	Δρ_max = 0.55 e Å⁻³
5212 reflections	Δρ_min = −0.55 e Å⁻³
290 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.93528 (19)	−0.0624 (3)	0.20557 (10)	0.0443 (6)
C2	0.8927 (2)	0.0321 (4)	0.23253 (11)	0.0603 (9)
H2	0.9211	0.1084	0.2423	0.072*
C3	0.8070 (3)	0.0097 (5)	0.24438 (14)	0.0821 (13)
H3	0.7772	0.0714	0.2625	0.099*
C4	0.7651 (3)	−0.1032 (6)	0.22961 (16)	0.0911 (14)
H4	0.7071	−0.1165	0.2376	0.109*
C5	0.8074 (3)	−0.1944 (5)	0.20365 (15)	0.0873 (14)
H5	0.7784	−0.2704	0.1940	0.105*
C6	0.8939 (2)	−0.1764 (4)	0.19114 (12)	0.0632 (9)
H6	0.9232	−0.2397	0.1734	0.076*
C7	0.98916 (17)	−0.0076 (3)	0.09633 (9)	0.0385 (6)
C8	1.00292 (18)	−0.1328 (3)	0.07857 (10)	0.0447 (7)
H8	1.0426	−0.1908	0.0921	0.054*
C9	0.95349 (18)	−0.1667 (3)	0.03908 (9)	0.0404 (6)
C10	0.87808 (19)	−0.2665 (3)	−0.03036 (10)	0.0432 (6)
C11	0.85167 (18)	−0.1409 (3)	−0.02240 (10)	0.0434 (6)
H11	0.8101	−0.0985	−0.0408	0.052*
C12	0.89407 (17)	−0.0797 (3)	0.01716 (9)	0.0403 (6)
C13	0.88459 (18)	0.0474 (3)	0.03532 (9)	0.0415 (6)
H13	0.8474	0.1075	0.0208	0.050*
C14	0.93126 (16)	0.0831 (3)	0.07524 (9)	0.0379 (6)
C15	0.93339 (17)	0.2031 (3)	0.10301 (9)	0.0395 (6)
C16	0.88881 (19)	0.3216 (3)	0.09834 (10)	0.0459 (7)
H16	0.8497	0.3349	0.0737	0.055*
C17	0.9044 (2)	0.4192 (3)	0.13154 (11)	0.0491 (7)
C18	0.9644 (2)	0.4001 (3)	0.16782 (11)	0.0528 (8)
H18	0.9740	0.4676	0.1896	0.063*
C19	1.0099 (2)	0.2840 (3)	0.17224 (10)	0.0501 (7)
H19	1.0509	0.2723	0.1961	0.060*
C20	0.99236 (17)	0.1851 (3)	0.13975 (9)	0.0417 (6)
C21	0.85065 (19)	−0.3600 (3)	−0.06662 (10)	0.0450 (6)
C22	0.89216 (19)	−0.4794 (3)	−0.08041 (10)	0.0460 (6)
H22	0.9418	−0.5142	−0.0664	0.055*
C23	0.8466 (2)	−0.5371 (3)	−0.11860 (12)	0.0569 (8)
H23	0.8657	−0.6131	−0.1339	0.068*
C24	0.7753 (2)	−0.4750 (4)	−0.13083 (13)	0.0664 (9)
H24	0.7385	−0.5036	−0.1548	0.080*
C25	0.7922 (3)	0.5579 (4)	0.10138 (15)	0.0769 (11)
H25A	0.8090	0.5441	0.0690	0.115*
H25B	0.7699	0.6459	0.1050	0.115*
H25C	0.7481	0.4953	0.1099	0.115*
N1	1.02958 (15)	0.0539 (2)	0.13643 (8)	0.0421 (5)
O1	1.08087 (14)	−0.1554 (2)	0.17329 (8)	0.0562 (6)
O2	1.08494 (15)	0.0508 (2)	0.21908 (8)	0.0604 (6)
O3	0.86577 (17)	0.5408 (2)	0.13127 (9)	0.0695 (7)
S1	1.04166 (5)	−0.03348 (8)	0.18631 (2)	0.0445 (2)
S2	0.95684 (5)	−0.31754 (8)	0.01006 (3)	0.0507 (2)
S3	0.75741 (7)	−0.33734 (10)	−0.09832 (4)	0.0750 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0485 (16)	0.0515 (16)	0.0329 (13)	0.0051 (13)	−0.0020 (11)	0.0074 (12)
C2	0.073 (2)	0.063 (2)	0.0449 (17)	0.0128 (17)	0.0092 (16)	0.0052 (15)
C3	0.085 (3)	0.096 (3)	0.065 (2)	0.036 (3)	0.031 (2)	0.021 (2)
C4	0.060 (2)	0.137 (4)	0.076 (3)	−0.010 (3)	0.019 (2)	0.016 (3)
C5	0.074 (3)	0.118 (4)	0.070 (3)	−0.037 (3)	0.020 (2)	−0.010 (2)
C6	0.067 (2)	0.073 (2)	0.0502 (18)	−0.0099 (18)	0.0100 (16)	−0.0031 (16)
C7	0.0345 (12)	0.0513 (16)	0.0297 (12)	−0.0015 (11)	0.0001 (10)	0.0009 (11)
C8	0.0442 (16)	0.0526 (17)	0.0372 (14)	0.0062 (13)	−0.0056 (12)	−0.0003 (12)
C9	0.0427 (14)	0.0433 (15)	0.0353 (13)	0.0000 (11)	0.0009 (11)	0.0000 (11)
C10	0.0455 (15)	0.0455 (15)	0.0386 (14)	−0.0005 (12)	−0.0039 (11)	0.0001 (12)
C11	0.0440 (15)	0.0464 (15)	0.0397 (14)	0.0008 (12)	−0.0085 (12)	0.0007 (12)
C12	0.0392 (14)	0.0467 (15)	0.0349 (13)	−0.0013 (11)	−0.0007 (11)	0.0003 (11)
C13	0.0398 (14)	0.0472 (15)	0.0376 (13)	0.0036 (12)	−0.0050 (11)	−0.0018 (12)
C14	0.0347 (13)	0.0459 (15)	0.0331 (13)	−0.0014 (11)	0.0012 (10)	−0.0010 (11)
C15	0.0373 (13)	0.0477 (15)	0.0335 (13)	−0.0042 (11)	0.0007 (10)	−0.0019 (11)
C16	0.0427 (15)	0.0526 (17)	0.0425 (15)	−0.0014 (13)	−0.0065 (12)	−0.0058 (13)
C17	0.0470 (15)	0.0495 (17)	0.0508 (17)	0.0020 (13)	−0.0015 (13)	−0.0084 (13)
C18	0.0599 (19)	0.0549 (18)	0.0437 (16)	−0.0056 (15)	−0.0068 (14)	−0.0108 (14)
C19	0.0535 (17)	0.0579 (18)	0.0388 (15)	−0.0058 (14)	−0.0109 (13)	−0.0043 (13)
C20	0.0381 (14)	0.0500 (16)	0.0370 (14)	−0.0040 (12)	−0.0011 (11)	−0.0007 (12)
C21	0.0501 (14)	0.0442 (15)	0.0407 (14)	−0.0049 (12)	−0.0022 (10)	0.0010 (12)
C22	0.0426 (15)	0.0519 (17)	0.0434 (15)	0.0052 (12)	−0.0069 (11)	−0.0041 (12)
C23	0.065 (2)	0.0474 (17)	0.0579 (18)	−0.0049 (15)	−0.0049 (14)	−0.0143 (14)
C24	0.067 (2)	0.065 (2)	0.067 (2)	−0.0017 (18)	−0.0189 (17)	−0.0188 (18)
C25	0.080 (3)	0.068 (2)	0.082 (3)	0.024 (2)	−0.022 (2)	−0.013 (2)
N1	0.0422 (12)	0.0502 (14)	0.0337 (11)	−0.0010 (10)	−0.0041 (9)	0.0006 (10)
O1	0.0533 (13)	0.0639 (13)	0.0514 (12)	0.0212 (11)	−0.0061 (10)	−0.0004 (10)
O2	0.0627 (14)	0.0726 (15)	0.0460 (12)	−0.0020 (11)	−0.0226 (10)	−0.0019 (11)
O3	0.0739 (16)	0.0571 (14)	0.0775 (17)	0.0132 (12)	−0.0235 (13)	−0.0201 (12)
S1	0.0414 (4)	0.0569 (5)	0.0353 (4)	0.0058 (3)	−0.0090 (3)	0.0010 (3)
S2	0.0622 (5)	0.0464 (4)	0.0435 (4)	0.0082 (3)	−0.0120 (3)	−0.0020 (3)
S3	0.0713 (6)	0.0670 (6)	0.0867 (7)	0.0164 (5)	−0.0298 (5)	−0.0227 (5)

Geometric parameters (Å, º) top

C1—C6	1.380 (5)	C14—C15	1.446 (4)
C1—C2	1.388 (4)	C15—C16	1.389 (4)
C1—S1	1.750 (3)	C15—C20	1.390 (4)
C2—C3	1.379 (6)	C16—C17	1.383 (4)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.376 (7)	C17—O3	1.368 (4)
C3—H3	0.9300	C17—C18	1.393 (4)
C4—C5	1.347 (7)	C18—C19	1.374 (5)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.388 (5)	C19—C20	1.385 (4)
C5—H5	0.9300	C19—H19	0.9300
C6—H6	0.9300	C20—N1	1.449 (4)
C7—C8	1.379 (4)	C21—C22	1.422 (4)
C7—C14	1.411 (4)	C21—S3	1.707 (3)
C7—N1	1.434 (3)	C22—C23	1.413 (4)
C8—C9	1.393 (4)	C22—H22	0.9300
C8—H8	0.9300	C23—C24	1.311 (5)
C9—C12	1.412 (4)	C23—H23	0.9300
C9—S2	1.734 (3)	C24—S3	1.692 (4)
C10—C11	1.354 (4)	C24—H24	0.9300
C10—C21	1.457 (4)	C25—O3	1.422 (4)
C10—S2	1.743 (3)	C25—H25A	0.9600
C11—C12	1.434 (4)	C25—H25B	0.9600
C11—H11	0.9300	C25—H25C	0.9600
C12—C13	1.394 (4)	N1—S1	1.674 (2)
C13—C14	1.384 (4)	O1—S1	1.422 (2)
C13—H13	0.9300	O2—S1	1.424 (2)

C6—C1—C2	121.4 (3)	C17—C16—C15	117.9 (3)
C6—C1—S1	118.7 (2)	C17—C16—H16	121.1
C2—C1—S1	119.8 (3)	C15—C16—H16	121.1
C3—C2—C1	118.1 (4)	O3—C17—C16	124.4 (3)
C3—C2—H2	121.0	O3—C17—C18	114.6 (3)
C1—C2—H2	121.0	C16—C17—C18	121.0 (3)
C4—C3—C2	120.8 (4)	C19—C18—C17	121.5 (3)
C4—C3—H3	119.6	C19—C18—H18	119.2
C2—C3—H3	119.6	C17—C18—H18	119.2
C5—C4—C3	120.5 (4)	C18—C19—C20	117.4 (3)
C5—C4—H4	119.7	C18—C19—H19	121.3
C3—C4—H4	119.7	C20—C19—H19	121.3
C4—C5—C6	120.8 (4)	C19—C20—C15	121.8 (3)
C4—C5—H5	119.6	C19—C20—N1	128.9 (3)
C6—C5—H5	119.6	C15—C20—N1	109.3 (2)
C1—C6—C5	118.5 (4)	C22—C21—C10	127.9 (3)
C1—C6—H6	120.7	C22—C21—S3	110.4 (2)
C5—C6—H6	120.7	C10—C21—S3	121.7 (2)
C8—C7—C14	122.8 (2)	C23—C22—C21	109.7 (3)
C8—C7—N1	128.3 (2)	C23—C22—H22	125.1
C14—C7—N1	108.9 (2)	C21—C22—H22	125.1
C7—C8—C9	115.7 (3)	C24—C23—C22	114.7 (3)
C7—C8—H8	122.2	C24—C23—H23	122.7
C9—C8—H8	122.2	C22—C23—H23	122.7
C8—C9—C12	123.4 (3)	C23—C24—S3	112.9 (3)
C8—C9—S2	125.4 (2)	C23—C24—H24	123.6
C12—C9—S2	111.2 (2)	S3—C24—H24	123.6
C11—C10—C21	129.8 (3)	O3—C25—H25A	109.5
C11—C10—S2	112.2 (2)	O3—C25—H25B	109.5
C21—C10—S2	118.0 (2)	H25A—C25—H25B	109.5
C10—C11—C12	113.5 (3)	O3—C25—H25C	109.5
C10—C11—H11	123.3	H25A—C25—H25C	109.5
C12—C11—H11	123.3	H25B—C25—H25C	109.5
C13—C12—C9	118.9 (2)	C7—N1—C20	106.1 (2)
C13—C12—C11	129.6 (3)	C7—N1—S1	118.85 (19)
C9—C12—C11	111.5 (2)	C20—N1—S1	118.30 (18)
C14—C13—C12	119.1 (3)	C17—O3—C25	117.3 (3)
C14—C13—H13	120.5	O1—S1—O2	119.31 (14)
C12—C13—H13	120.5	O1—S1—N1	106.77 (13)
C13—C14—C7	120.1 (3)	O2—S1—N1	106.37 (13)
C13—C14—C15	132.2 (3)	O1—S1—C1	109.39 (15)
C7—C14—C15	107.7 (2)	O2—S1—C1	109.64 (15)
C16—C15—C20	120.4 (3)	N1—S1—C1	104.24 (12)
C16—C15—C14	131.6 (2)	C9—S2—C10	91.58 (13)
C20—C15—C14	108.0 (2)	C24—S3—C21	92.11 (16)

C6—C1—C2—C3	−0.5 (5)	C16—C15—C20—C19	−1.1 (4)
S1—C1—C2—C3	175.8 (3)	C14—C15—C20—C19	179.0 (3)
C1—C2—C3—C4	−0.3 (6)	C16—C15—C20—N1	−179.9 (2)
C2—C3—C4—C5	0.7 (7)	C14—C15—C20—N1	0.2 (3)
C3—C4—C5—C6	−0.2 (7)	C11—C10—C21—C22	165.1 (3)
C2—C1—C6—C5	0.8 (5)	S2—C10—C21—C22	−14.8 (4)
S1—C1—C6—C5	−175.4 (3)	C11—C10—C21—S3	−16.4 (5)
C4—C5—C6—C1	−0.5 (6)	S2—C10—C21—S3	163.72 (17)
C14—C7—C8—C9	−2.2 (4)	C10—C21—C22—C23	−177.0 (3)
N1—C7—C8—C9	179.5 (3)	S3—C21—C22—C23	4.4 (3)
C7—C8—C9—C12	1.4 (4)	C21—C22—C23—C24	−3.9 (4)
C7—C8—C9—S2	−179.3 (2)	C22—C23—C24—S3	1.7 (4)
C21—C10—C11—C12	179.9 (3)	C8—C7—N1—C20	179.9 (3)
S2—C10—C11—C12	−0.2 (3)	C14—C7—N1—C20	1.4 (3)
C8—C9—C12—C13	0.8 (4)	C8—C7—N1—S1	−43.8 (4)
S2—C9—C12—C13	−178.6 (2)	C14—C7—N1—S1	137.7 (2)
C8—C9—C12—C11	−179.5 (3)	C19—C20—N1—C7	−179.6 (3)
S2—C9—C12—C11	1.2 (3)	C15—C20—N1—C7	−1.0 (3)
C10—C11—C12—C13	179.0 (3)	C19—C20—N1—S1	43.8 (4)
C10—C11—C12—C9	−0.7 (4)	C15—C20—N1—S1	−137.5 (2)
C9—C12—C13—C14	−2.3 (4)	C16—C17—O3—C25	13.9 (5)
C11—C12—C13—C14	178.0 (3)	C18—C17—O3—C25	−167.9 (3)
C12—C13—C14—C7	1.6 (4)	C7—N1—S1—O1	50.2 (2)
C12—C13—C14—C15	−177.5 (3)	C20—N1—S1—O1	−178.7 (2)
C8—C7—C14—C13	0.7 (4)	C7—N1—S1—O2	178.7 (2)
N1—C7—C14—C13	179.3 (2)	C20—N1—S1—O2	−50.3 (2)
C8—C7—C14—C15	−179.9 (2)	C7—N1—S1—C1	−65.5 (2)
N1—C7—C14—C15	−1.3 (3)	C20—N1—S1—C1	65.6 (2)
C13—C14—C15—C16	0.0 (5)	C6—C1—S1—O1	−22.2 (3)
C7—C14—C15—C16	−179.2 (3)	C2—C1—S1—O1	161.4 (2)
C13—C14—C15—C20	179.9 (3)	C6—C1—S1—O2	−154.8 (3)
C7—C14—C15—C20	0.7 (3)	C2—C1—S1—O2	28.9 (3)
C20—C15—C16—C17	−0.7 (4)	C6—C1—S1—N1	91.6 (3)
C14—C15—C16—C17	179.1 (3)	C2—C1—S1—N1	−84.7 (3)
C15—C16—C17—O3	179.6 (3)	C8—C9—S2—C10	179.6 (3)
C15—C16—C17—C18	1.5 (5)	C12—C9—S2—C10	−1.1 (2)
O3—C17—C18—C19	−178.7 (3)	C11—C10—S2—C9	0.7 (2)
C16—C17—C18—C19	−0.4 (5)	C21—C10—S2—C9	−179.4 (2)
C17—C18—C19—C20	−1.4 (5)	C23—C24—S3—C21	0.9 (3)
C18—C19—C20—C15	2.2 (4)	C22—C21—S3—C24	−3.1 (3)
C18—C19—C20—N1	−179.3 (3)	C10—C21—S3—C24	178.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1	0.93	2.57	2.930 (4)	103
C8—H8···O1	0.93	2.39	2.940 (3)	117
C19—H19···O2	0.93	2.39	2.943 (4)	118
C22—H22···S2ⁱ	0.93	2.80	3.684 (3)	158

Symmetry code: (i) −x+2, −y−1, −z.

Experimental details

Crystal data
Chemical formula	C₂₅H₁₇NO₃S₃
M_r	475.58
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	295
a, b, c (Å)	15.3900 (12), 10.1269 (7), 28.233 (2)
V (Å³)	4400.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEX2 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.914, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	25628, 5212, 3570
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.175, 1.04
No. of reflections	5212
No. of parameters	290
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.55

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1	0.93	2.57	2.930 (4)	103
C8—H8···O1	0.93	2.39	2.940 (3)	117
C19—H19···O2	0.93	2.39	2.943 (4)	118
C22—H22···S2ⁱ	0.93	2.80	3.684 (3)	158

Symmetry code: (i) −x+2, −y−1, −z.

Acknowledgements

The authors acknowledge the Sophisticated Analytical Instrument Facility, Indian Institute of Technology, Madras, for the data collection.

References

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. CrossRef Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chakkaravarthi, G., Dhayalan, V., Mohanakrishnan, A. K. & Manivannan, V. (2008a). Acta Cryst. E64, o1667–o1668. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Chakkaravarthi, G., Dhayalan, V., Mohanakrishnan, A. K. & Manivannan, V. (2008b). Acta Cryst. E64, o1712–o1713. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Diaz, J. L., Villacampa, B., Lopez-Calahorra, F. & Velasco, D. (2002). Chem. Mater. 14, 2240–2251. Web of Science CrossRef CAS Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Govindasamy, L., Velmurugan, D., Ravikumar, K. & Mohanakrishnan, A. K. (1998). Acta Cryst. C54, 277–279. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Hökelek, T., Gündüz, H., Patir, S. & Uludaug, N. (1998). Acta Cryst. C54, 1297–1299. Web of Science CSD CrossRef IUCr Journals Google Scholar
Itoigawa, M., Kashiwada, Y., Ito, C., Furukawa, H., Tachibana, Y., Bastow, K. F. & Lee, K. H. (2000). J. Nat. Prod. 63, 893–897. Web of Science CrossRef PubMed CAS Google Scholar
Ramsewak, R. S., Nair, M. G., Strasburg, G. M., DeWitt, D. L. & Nitiss, J. L. (1999). J. Agric. Food Chem. 47, 444–447. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tachibana, Y., Kikuzaki, H., Lajis, N. H. & Nakatani, N. (2001). J. Agric. Food Chem. 49, 5589–5594. Web of Science CrossRef PubMed CAS Google Scholar
Zhang, Q., Chen, J., Cheng, Y., Wang, L., Ma, D., Jing, X. & Wang, F. (2004). J. Mater. Chem. 14, 895–900. Web of Science CrossRef CAS Google Scholar