4-Methyl-9-[(4-methyl­phen­yl)sulfon­yl]thio­pyrano[3,4-b]indole-3(9H)-thione

Dassonneville, B.; Schollmeyer, D.; Witulski, B.; Detert, H.

doi:10.1107/S1600536810038201

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2665

doi:10.1107/S1600536810038201

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4-Methyl-9-[(4-methylphenyl)sulfonyl]thiopyrano[3,4-b]indole-3(9H)-thione

Benjamin Dassonneville,^a Dieter Schollmeyer,^a Bernhard Witulski ^b and Heiner Detert ^a ^*

^aUniversity Mainz, Duesbergweg 10-14, 55099 Mainz, Germany, and ^bLaboratoire de Chimie Moléculaire et Thio-organique, UMR 6507, ENSICAEN, 6 Boulevard Maréchal Juin, 14050 Caen, France
^*Correspondence e-mail: detert@uni-mainz.de

(Received 23 September 2010; accepted 24 September 2010; online 30 September 2010)

The title compound, C₁₉H₁₅NO₂S₃, is the first example of a dithia analogue of pyrano[3,4-b]indolone. The almost planar thiopyranoindolethione ring system (r.m.s. deviation for all non-H atoms = 0.030 Å) makes a dihedral angle of 80.70 (8)° with the p-tolyl ring. In the crystal, molecules are connected via C—H⋯O hydrogen bonds into two chains along the b axis. These chains are connected via π–π interactions between symmetry-related thiopyranoindolethione ring systems [centroid–centroid distance = 3.588 (1) Å].

Related literature

The title compound was synthesized as part of a larger project focusing on metal-catalysed transformations of tethered alkynyl-ynamides to carbazoles (Witulski & Alayrac, 2002 ) and to carbolines and other heteroannulated indoles (Nissen, 2008 ; Dassonneville, 2010 ). The reactivity of such an annulated thiopyranothione could be similar to the respective pyrano[3,4-b]indolone, well known as stable equivalents of indoloquinodimethanes (Plieninger et al., 1964 ) and valuable intermediates for the synthesis of various heteroannulated indoles, see, for example: Livadiotou et al. (2009 ).

Experimental

Crystal data

C₁₉H₁₅NO₂S₃
M_r = 385.50
Monoclinic, P 2₁ /n
a = 13.2530 (4) Å
b = 8.2423 (3) Å
c = 15.4500 (16) Å
β = 96.124 (3)°
V = 1678.05 (19) Å³
Z = 4
Cu Kα radiation
μ = 4.15 mm⁻¹
T = 193 K
0.60 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: numerical (de Meulenaer & Tompa, 1965 ) T_min = 0.42, T_max = 0.70
3167 measured reflections
3167 independent reflections
2714 reflections with I > 2σ(I)
3 standard reflections every 60 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.04
3167 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯O15ⁱ	0.95	2.50	3.387 (3)	155
C22—H22⋯O16ⁱⁱ	0.95	2.59	3.116 (3)	116
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038201/bt5362sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038201/bt5362Isup2.hkl

checkCIF report

Comment top

The title compound is formed via a rhodium-catalyzed [2 + 2+2] cycloaddition of a tethered alkynyl-ynamide and carbon disulfide. This unprecedented thiopyranoindolethione is obtained as dark violet crystals. The crystal structure of the title compound forms a network built by two chains along the b axis connected via hydrogen bonds C21—H21···O15 (2.50 Å) and C22—H21···O16 (2.59 Å). These chains are connected via π-π-interactions of two thiopyranoindolethiones related by a center of symmetry [distance between centroids 3.588 (1) Å].

The tricyclic framework is essentially planar with torsion angles of about 2.1 ° or less in the benzene moiety and up to 5.9 ° in the thiopyrane unit. The torsion angle around the biphenyl bond amounts to 176.0 (2) ° (C6,C7,C8,C13). Whereas the N—C bonds in the pyrrole ring are nearly identical, the C—C bond lengths increase in the sequence C2—C7, C7—C8, C8—C13. With 1.459 (3) Å, the biphenyl bond C7—C8 is significantly longer than C2—C3 (1.384 (3) Å) and C8—C13 (1.443 (3) Å). The thiocarbonyl bond length is about 1.668 (2) Å, much shorter than the C—S single bonds with 1.729 (2) Å (C10—S11) and 1.702 (2) Å (S11—C12). Due to steric repulsion of methyl and thiocarbonyl, the S24—C10—S11 bond angle is reduced to 113.07 (13) ° and the C10—S11—C12 bond angle is only 107.07 (11) °.

Related literature top

The title compound was synthesized as part of a larger project focusing on metal-catalysed transformations of tethered alkynyl-ynamides to carbazoles (Witulski & Alayrac, 2002) and to carbolines and other heteroannulated indoles (Nissen, 2008; Dassonneville, 2010). The reactivity of such an annulated thiopyranothione could be similar to the respective pyrano[3,4-b]indolone, well known as stable equivalents of indoloquinodimethanes (Plieninger et al., 1964) and valuable intermediates for the synthesis of various heteroannulated indoles, see, for example: Livadiotou et al. (2009).

Experimental top

The title compound was prepared from 2-(propynyl)-N-ethynyl-N-[(4-methylphenyl)sulfonyl)]benzenamine (Witulski & Alayrac, 2002)) as follows: Under Argon (Ar), BINAP (15.6 mg, 0.025 mmol, 10 mol%) and [RhCl(C₈H₁₄)₂]₂ (6.1 mg, 0.0087 mmol, 3.5 mol%) are dissolved in degassed CH₂Cl₂ (3.0 ml) in a Schlenk tube, and the mixture is stirred at room temperature for 5 min. H₂ is then introduced to the resulting solution. After stirring at room temperature for 0.5 h, the resulting solution is concentrated to dryness and the residue dissolved in dichloroethane (DCE) (3.0 ml). To this solution is added dropwise over 1 min a solution of the alkynyl-ynamide (0.25 mmol) and CS₂ (150 µL, 2.5 mmol, 10 equiv.) in DCE (5.0 ml). Undissolved substrate is dissolved by addition of DCE (2x1.0 ml), added to the solution and the mixture is heated to 353 K. After completion of the reaction (3 h, TLC), the solvent is removed and the residue is purified by column chromatography (Al₂O₃, Petroleum ether/Ethyl acetate, 95/5). Violet crystals of the title compound suitable for X-ray analysis were obtained by crystallization from CH₂Cl₂/Petroleum ether.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: CORINC (Dräger & Gattow, 1971); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the packing diagram showing the hydrogen bonds and the π-π-interactions.

4-Methyl-9-[(4-methylphenyl)sulfonyl]thiopyrano[3,4-b]indole- 3(9H)-thione top

Crystal data top

C₁₉H₁₅NO₂S₃	F(000) = 800
M_r = 385.50	D_x = 1.526 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 13.2530 (4) Å	θ = 60–70°
b = 8.2423 (3) Å	µ = 4.15 mm⁻¹
c = 15.4500 (16) Å	T = 193 K
β = 96.124 (3)°	Needle, violet
V = 1678.05 (19) Å³	0.60 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2714 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.000
Graphite monochromator	θ_max = 69.9°, θ_min = 4.2°
ω/2θ scans	h = 0→16
Absorption correction: numerical (de Meulenaer & Tompa, 1965)	k = 0→10
T_min = 0.42, T_max = 0.70	l = −18→18
3167 measured reflections	3 standard reflections every 60 min
3167 independent reflections	intensity decay: 2%

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: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.053P)² + 0.8161P] where P = (F_o² + 2F_c²)/3
3167 reflections	(Δ/σ)_max < 0.001
228 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₉H₁₅NO₂S₃	V = 1678.05 (19) Å³
M_r = 385.50	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 13.2530 (4) Å	µ = 4.15 mm⁻¹
b = 8.2423 (3) Å	T = 193 K
c = 15.4500 (16) Å	0.60 × 0.10 × 0.10 mm
β = 96.124 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2714 reflections with I > 2σ(I)
Absorption correction: numerical (de Meulenaer & Tompa, 1965)	R_int = 0.000
T_min = 0.42, T_max = 0.70	3 standard reflections every 60 min
3167 measured reflections	intensity decay: 2%
3167 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.04	Δρ_max = 0.42 e Å⁻³
3167 reflections	Δρ_min = −0.36 e Å⁻³
228 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

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

	x	y	z	U_iso*/U_eq
N1	0.30393 (13)	0.4410 (2)	0.44134 (12)	0.0228 (4)
C2	0.29369 (15)	0.4317 (3)	0.53192 (14)	0.0230 (4)
C3	0.21571 (17)	0.4930 (3)	0.57513 (16)	0.0293 (5)
H3	0.1611	0.5518	0.5451	0.035*
C4	0.22049 (18)	0.4654 (3)	0.66365 (16)	0.0336 (5)
H4	0.1683	0.5064	0.6952	0.040*
C5	0.30000 (19)	0.3790 (3)	0.70717 (16)	0.0346 (5)
H5	0.3005	0.3596	0.7678	0.042*
C6	0.37865 (18)	0.3204 (3)	0.66405 (15)	0.0309 (5)
H6	0.4333	0.2625	0.6947	0.037*
C7	0.37639 (15)	0.3478 (2)	0.57428 (14)	0.0222 (4)
C8	0.44351 (15)	0.3017 (2)	0.50942 (14)	0.0211 (4)
C9	0.53663 (16)	0.2244 (3)	0.52013 (15)	0.0243 (4)
C10	0.58968 (16)	0.1801 (3)	0.44741 (16)	0.0263 (5)
S11	0.54433 (4)	0.23832 (8)	0.34297 (4)	0.03407 (17)
C12	0.43366 (17)	0.3397 (3)	0.34993 (15)	0.0303 (5)
H12	0.3984	0.3847	0.2987	0.036*
C13	0.39482 (15)	0.3576 (2)	0.42680 (14)	0.0217 (4)
S14	0.20305 (4)	0.46546 (6)	0.36740 (4)	0.02438 (15)
O15	0.15035 (12)	0.60556 (19)	0.39288 (12)	0.0353 (4)
O16	0.24145 (12)	0.4613 (2)	0.28475 (11)	0.0367 (4)
C17	0.12629 (15)	0.2950 (2)	0.37845 (13)	0.0194 (4)
C18	0.02728 (16)	0.3153 (3)	0.39707 (15)	0.0268 (5)
H18	0.0018	0.4205	0.4072	0.032*
C19	−0.03435 (16)	0.1799 (3)	0.40080 (15)	0.0276 (5)
H19	−0.1023	0.1931	0.4137	0.033*
C20	0.00193 (16)	0.0253 (3)	0.38587 (14)	0.0238 (4)
C21	0.10251 (16)	0.0078 (3)	0.36982 (14)	0.0254 (5)
H21	0.1288	−0.0977	0.3619	0.031*
C22	0.16513 (16)	0.1414 (3)	0.36515 (14)	0.0252 (5)
H22	0.2335	0.1283	0.3531	0.030*
C23	−0.06630 (18)	−0.1206 (3)	0.38685 (16)	0.0301 (5)
H23A	−0.1058	−0.1136	0.4368	0.045*
H23B	−0.0250	−0.2195	0.3914	0.045*
H23C	−0.1125	−0.1236	0.3329	0.045*
S24	0.69645 (4)	0.07193 (8)	0.45140 (5)	0.04028 (18)
C25	0.58643 (19)	0.1818 (3)	0.60888 (17)	0.0365 (6)
H25A	0.5844	0.2758	0.6475	0.055*
H25B	0.6572	0.1509	0.6048	0.055*
H25C	0.5503	0.0908	0.6324	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0188 (8)	0.0218 (9)	0.0278 (9)	0.0008 (7)	0.0021 (7)	0.0015 (7)
C2	0.0217 (10)	0.0168 (10)	0.0303 (11)	−0.0057 (8)	0.0021 (8)	−0.0027 (8)
C3	0.0239 (11)	0.0226 (11)	0.0419 (13)	−0.0002 (9)	0.0058 (9)	−0.0042 (10)
C4	0.0323 (12)	0.0306 (13)	0.0397 (13)	−0.0057 (10)	0.0124 (10)	−0.0098 (10)
C5	0.0410 (13)	0.0341 (13)	0.0299 (12)	−0.0074 (11)	0.0089 (10)	−0.0040 (10)
C6	0.0328 (12)	0.0296 (12)	0.0300 (11)	−0.0031 (10)	0.0023 (9)	0.0013 (10)
C7	0.0225 (10)	0.0144 (10)	0.0295 (11)	−0.0048 (8)	0.0021 (8)	−0.0003 (8)
C8	0.0215 (10)	0.0142 (9)	0.0276 (10)	−0.0039 (8)	0.0021 (8)	0.0010 (8)
C9	0.0207 (10)	0.0166 (10)	0.0354 (11)	−0.0020 (8)	0.0014 (8)	0.0027 (9)
C10	0.0192 (10)	0.0168 (10)	0.0435 (13)	−0.0028 (8)	0.0057 (9)	0.0016 (9)
S11	0.0296 (3)	0.0377 (3)	0.0369 (3)	0.0052 (2)	0.0126 (2)	0.0018 (3)
C12	0.0257 (11)	0.0360 (13)	0.0296 (11)	0.0038 (10)	0.0044 (9)	0.0049 (10)
C13	0.0185 (9)	0.0172 (10)	0.0293 (11)	−0.0017 (8)	0.0020 (8)	0.0021 (8)
S14	0.0203 (3)	0.0180 (3)	0.0340 (3)	−0.00007 (19)	−0.0006 (2)	0.0073 (2)
O15	0.0286 (8)	0.0155 (8)	0.0602 (11)	0.0028 (7)	−0.0026 (8)	0.0043 (7)
O16	0.0284 (8)	0.0483 (11)	0.0328 (9)	−0.0043 (8)	0.0003 (7)	0.0169 (8)
C17	0.0197 (9)	0.0135 (10)	0.0245 (10)	0.0000 (8)	0.0005 (8)	0.0010 (8)
C18	0.0218 (10)	0.0175 (11)	0.0408 (12)	0.0042 (8)	0.0027 (9)	−0.0034 (9)
C19	0.0217 (10)	0.0225 (11)	0.0394 (12)	0.0003 (9)	0.0066 (9)	−0.0045 (9)
C20	0.0273 (11)	0.0193 (11)	0.0241 (10)	−0.0005 (9)	−0.0006 (8)	−0.0012 (8)
C21	0.0295 (11)	0.0158 (10)	0.0305 (11)	0.0054 (9)	0.0008 (9)	−0.0043 (9)
C22	0.0224 (10)	0.0233 (11)	0.0301 (11)	0.0047 (9)	0.0045 (8)	−0.0014 (9)
C23	0.0346 (12)	0.0206 (11)	0.0345 (12)	−0.0052 (9)	0.0011 (9)	−0.0017 (9)
S24	0.0255 (3)	0.0312 (3)	0.0654 (4)	0.0079 (2)	0.0110 (3)	0.0038 (3)
C25	0.0316 (12)	0.0363 (14)	0.0401 (13)	0.0056 (11)	−0.0034 (10)	0.0049 (11)

Geometric parameters (Å, º) top

N1—C2	1.422 (3)	C17—C22	1.390 (3)
N1—C13	1.425 (3)	C18—C19	1.388 (3)
N1—S14	1.6756 (18)	C19—C20	1.390 (3)
C2—C3	1.384 (3)	C20—C21	1.389 (3)
C2—C7	1.398 (3)	C20—C23	1.505 (3)
C3—C4	1.381 (3)	C21—C22	1.385 (3)
C4—C5	1.385 (4)	C3—H3	0.9500
C5—C6	1.383 (3)	C4—H4	0.9500
C6—C7	1.403 (3)	C5—H5	0.9500
C7—C8	1.459 (3)	C6—H6	0.9500
C8—C9	1.383 (3)	C12—H12	0.9500
C8—C13	1.443 (3)	C18—H18	0.9500
C9—C10	1.435 (3)	C19—H19	0.9500
C9—C25	1.499 (3)	C21—H21	0.9500
C10—S24	1.668 (2)	C22—H22	0.9500
C10—S11	1.729 (2)	C23—H23A	0.9800
S11—C12	1.702 (2)	C23—H23B	0.9800
C12—C13	1.352 (3)	C23—H23C	0.9800
S14—O16	1.4245 (18)	C25—H25A	0.9800
S14—O15	1.4265 (17)	C25—H25B	0.9800
S14—C17	1.754 (2)	C25—H25C	0.9800
C17—C18	1.383 (3)

C2—N1—C13	107.46 (17)	C18—C19—C20	121.0 (2)
C2—N1—S14	121.62 (14)	C21—C20—C19	118.7 (2)
C13—N1—S14	125.24 (15)	C21—C20—C23	120.5 (2)
C3—C2—C7	122.9 (2)	C19—C20—C23	120.8 (2)
C3—C2—N1	127.5 (2)	C22—C21—C20	121.2 (2)
C7—C2—N1	109.56 (18)	C21—C22—C17	118.86 (19)
C4—C3—C2	117.4 (2)	C2—C3—H3	121.00
C3—C4—C5	121.2 (2)	C4—C3—H3	121.00
C6—C5—C4	121.3 (2)	C3—C4—H4	119.00
C5—C6—C7	118.8 (2)	C5—C4—H4	119.00
C2—C7—C6	118.4 (2)	C4—C5—H5	119.00
C2—C7—C8	108.18 (18)	C6—C5—H5	119.00
C6—C7—C8	133.4 (2)	C5—C6—H6	121.00
C9—C8—C13	124.2 (2)	C7—C6—H6	121.00
C9—C8—C7	129.7 (2)	S11—C12—H12	119.00
C13—C8—C7	106.06 (17)	C13—C12—H12	119.00
C8—C9—C10	121.9 (2)	C17—C18—H18	120.00
C8—C9—C25	121.2 (2)	C19—C18—H18	120.00
C10—C9—C25	116.88 (19)	C18—C19—H19	119.00
C9—C10—S24	126.28 (18)	C20—C19—H19	120.00
C9—C10—S11	120.65 (16)	C20—C21—H21	119.00
S24—C10—S11	113.07 (13)	C22—C21—H21	119.00
C12—S11—C10	107.07 (11)	C17—C22—H22	121.00
C13—C12—S11	121.37 (18)	C21—C22—H22	121.00
C12—C13—N1	126.8 (2)	C20—C23—H23A	109.00
C12—C13—C8	124.5 (2)	C20—C23—H23B	109.00
N1—C13—C8	108.67 (18)	C20—C23—H23C	109.00
O16—S14—O15	119.95 (11)	H23A—C23—H23B	110.00
O16—S14—N1	105.83 (9)	H23A—C23—H23C	109.00
O15—S14—N1	106.73 (10)	H23B—C23—H23C	109.00
O16—S14—C17	109.53 (10)	C9—C25—H25A	110.00
O15—S14—C17	108.39 (10)	C9—C25—H25B	109.00
N1—S14—C17	105.43 (9)	C9—C25—H25C	109.00
C18—C17—C22	121.02 (19)	H25A—C25—H25B	109.00
C18—C17—S14	119.77 (16)	H25A—C25—H25C	109.00
C22—C17—S14	119.17 (16)	H25B—C25—H25C	109.00
C17—C18—C19	119.2 (2)

C13—N1—C2—C3	−178.6 (2)	S11—C12—C13—C8	3.1 (3)
S14—N1—C2—C3	−24.0 (3)	C2—N1—C13—C12	−178.9 (2)
C13—N1—C2—C7	1.1 (2)	S14—N1—C13—C12	27.6 (3)
S14—N1—C2—C7	155.80 (15)	C2—N1—C13—C8	−2.3 (2)
C7—C2—C3—C4	−1.5 (3)	S14—N1—C13—C8	−155.83 (15)
N1—C2—C3—C4	178.3 (2)	C9—C8—C13—C12	0.7 (3)
C2—C3—C4—C5	−0.3 (3)	C7—C8—C13—C12	179.3 (2)
C3—C4—C5—C6	1.5 (4)	C9—C8—C13—N1	−176.00 (19)
C4—C5—C6—C7	−0.9 (4)	C7—C8—C13—N1	2.6 (2)
C3—C2—C7—C6	2.1 (3)	C2—N1—S14—O16	−177.20 (16)
N1—C2—C7—C6	−177.71 (18)	C13—N1—S14—O16	−27.17 (19)
C3—C2—C7—C8	−179.74 (19)	C2—N1—S14—O15	53.96 (18)
N1—C2—C7—C8	0.5 (2)	C13—N1—S14—O15	−156.01 (17)
C5—C6—C7—C2	−0.8 (3)	C2—N1—S14—C17	−61.18 (18)
C5—C6—C7—C8	−178.5 (2)	C13—N1—S14—C17	88.86 (18)
C2—C7—C8—C9	176.6 (2)	O16—S14—C17—C18	−124.30 (18)
C6—C7—C8—C9	−5.6 (4)	O15—S14—C17—C18	8.3 (2)
C2—C7—C8—C13	−1.9 (2)	N1—S14—C17—C18	122.24 (18)
C6—C7—C8—C13	176.0 (2)	O16—S14—C17—C22	53.38 (19)
C13—C8—C9—C10	−5.5 (3)	O15—S14—C17—C22	−174.07 (17)
C7—C8—C9—C10	176.3 (2)	N1—S14—C17—C22	−60.09 (19)
C13—C8—C9—C25	175.0 (2)	C22—C17—C18—C19	−1.2 (3)
C7—C8—C9—C25	−3.2 (3)	S14—C17—C18—C19	176.40 (17)
C8—C9—C10—S24	−173.91 (17)	C17—C18—C19—C20	−0.2 (3)
C25—C9—C10—S24	5.6 (3)	C18—C19—C20—C21	2.1 (3)
C8—C9—C10—S11	5.9 (3)	C18—C19—C20—C23	−177.8 (2)
C25—C9—C10—S11	−174.60 (17)	C19—C20—C21—C22	−2.5 (3)
C9—C10—S11—C12	−2.1 (2)	C23—C20—C21—C22	177.3 (2)
S24—C10—S11—C12	177.70 (12)	C20—C21—C22—C17	1.2 (3)
C10—S11—C12—C13	−2.2 (2)	C18—C17—C22—C21	0.8 (3)
S11—C12—C13—N1	179.22 (17)	S14—C17—C22—C21	−176.89 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O15ⁱ	0.95	2.50	3.387 (3)	155
C22—H22···O16ⁱⁱ	0.95	2.59	3.116 (3)	116

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

Experimental details

Crystal data
Chemical formula	C₁₉H₁₅NO₂S₃
M_r	385.50
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	193
a, b, c (Å)	13.2530 (4), 8.2423 (3), 15.4500 (16)
β (°)	96.124 (3)
V (Å³)	1678.05 (19)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.15
Crystal size (mm)	0.60 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Numerical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.42, 0.70
No. of measured, independent and observed [I > 2σ(I)] reflections	3167, 3167, 2714
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.04
No. of reflections	3167
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.36

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Dräger & Gattow, 1971), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O15ⁱ	0.95	2.50	3.387 (3)	155
C22—H22···O16ⁱⁱ	0.95	2.59	3.116 (3)	116

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

References

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
Dassonneville, B. (2010). PhD thesis, University Mainz, Germany. Google Scholar
Dräger, M. & Gattow, G. (1971). Acta Chem. Scand. 25, 761–762. Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Livadiotou, D., Tsoleridis, C. A. & Stephanidou-Stephanatou, J. (2009). Synthesis, 15, 2579–2583. Google Scholar
Meulenaer, J. de & Tompa, H. (1965). Acta Cryst. 19, 1014–1018. CrossRef IUCr Journals Web of Science Google Scholar
Nissen, F. (2008). PhD thesis, University Mainz, Germany. Google Scholar
Plieninger, H., Mueller, W. & Weinerth, K. (1964). Chem. Ber. 97, 667–681. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Witulski, B. & Alayrac, C. (2002). Angew. Chem. Int. Ed. 41, 3281–3284. CrossRef CAS Google Scholar

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Volume 66| Part 10| October 2010| Page o2665

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