4-Methyl-9-[(4-methyl-phen-yl)sulfon-yl]thio-pyrano[3,4-b]indole-3(9H)-thione.

The title compound, C(19)H(15)NO(2)S(3), is the first example of a dithia analogue of pyrano[3,4-b]indolone. The almost planar thio-pyrano-indole-thione 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, mol-ecules are connected via C-H⋯O hydrogen bonds into two chains along the b axis. These chains are connected via π-π inter-actions between symmetry-related thio-pyrano-indole-thione 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 = 385.50

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.04

3167 reflections

228 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.36 e Å−3

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.

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

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

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

C19H15NO2S3	F(000) = 800
Mr = 385.50	Dx = 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

Enraf–Nonius CAD-4 diffractometer	2714 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.0000
graphite	θmax = 69.9°, θmin = 4.2°
ω/2θ scans	h = 0→16
Absorption correction: numerical (de Meulenaer & Tompa, 1965)	k = 0→10
Tmin = 0.42, Tmax = 0.70	l = −18→18
3167 measured reflections	3 standard reflections every 60 min
3167 independent reflections	intensity decay: 2%

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(Fo2) + (0.053P)2 + 0.8161P] where P = (Fo2 + 2Fc2)/3
3167 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) ; (ii) .