3,9-Dimethyl-2,3-dihydro-spiro-[carb-az-ole-1,2'-[1,3]dithio-lan]-4(9H)-one.

The title compound, C16H17NOS2, consists of a carbazole skeleton with methyl and dithiol-ane groups as substituents. In the indole ring system, the benzene and pyrrole rings are nearly coplanar, forming a dihedral angle of 1.02 (11)°. The cyclo-hexenone ring has a twisted conformation, while the dithiol-ane ring adopts an envelope conformation with one of the CH2 C atoms at the flap. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into supra-molecular chains nearly parallel to the c axis. These hydrogen bonds together with weak C-H⋯π inter-actions link the molecules into a three-dimensional supramolecular network.

Related literature

For tetra­hydro­carbazole systems present in the framework of a number of indole-type alkaloids of biological inter­est, see: Saxton (1983 ▶). For related structures, see: Hökelek et al. (1994 ▶, 1998 ▶, 1999 ▶, 2009 ▶); Patır et al. (1997 ▶); Hökelek & Patır (1999 ▶); Çaylak et al. (2007 ▶); Uludağ et al. (2009 ▶). For the isolation of carbazole alkaloids such as 3-methyl­carbazole and its several oxidized derivatives from taxonomically related higher plants, see: Chakraborty (1993 ▶); Bhattacharyya & Chakraborty (1987 ▶). For the use of 4-oxo-tetra­hydro­carbazole in the synthesis of anti­emetic drugs, central nervous system active drugs and NPY-1 antagonists, see: Littell & Allen (1973 ▶); Ping & Guoping (1997 ▶); Fabio et al. (2006 ▶); Kumar et al. (2008 ▶). For the use of 4-oxo-tetra­hydro­carbazole derivatives in the synthesis of indole alkaloids, see: Magnus et al. (1992 ▶); Ergün et al. (2000 ▶, 2002 ▶). For the synthesis of tetra­hydro­carbazolone-based anti­tumor active compounds and inhibitors of HIV integrase from 4-oxo-tetra­hydro­carbazoles, see: Li & Vince (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C16H17NOS2

M = 303.43

Orthorhombic,

a = 16.8163 (3) Å

b = 9.8407 (2) Å

c = 17.2913 (4) Å

V = 2861.44 (10) Å3

Z = 8

Mo Kα radiation

μ = 0.37 mm−1

T = 100 K

0.47 × 0.32 × 0.29 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.847, T max = 0.901

13394 measured reflections

3540 independent reflections

2912 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.075

wR(F 2) = 0.195

S = 1.05

3540 reflections

183 parameters

H-atom parameters constrained

Δρmax = 1.73 e Å−3

Δρmin = −1.08 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012) ▶ and PLATON (Spek, 2009) ▶.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007873/xu5690sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007873/xu5690Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813007873/xu5690Isup3.cml

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

C16H17NOS2	F(000) = 1280
Mr = 303.43	Dx = 1.409 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3799 reflections
a = 16.8163 (3) Å	θ = 2.7–28.2°
b = 9.8407 (2) Å	µ = 0.37 mm−1
c = 17.2913 (4) Å	T = 100 K
V = 2861.44 (10) Å3	Block, colorless
Z = 8	0.47 × 0.32 × 0.29 mm

Bruker Kappa APEXII CCD area-detector diffractometer	3540 independent reflections
Radiation source: fine-focus sealed tube	2912 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 28.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −22→22
Tmin = 0.847, Tmax = 0.901	k = −13→10
13394 measured reflections	l = −23→20

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.195	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0845P)2 + 10.7607P] where P = (Fo2 + 2Fc2)/3
3540 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 1.73 e Å−3
0 restraints	Δρmin = −1.08 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S1	0.92826 (5)	0.57718 (9)	0.92430 (5)	0.0250 (2)
S2	0.76350 (5)	0.48874 (9)	0.95846 (6)	0.0268 (2)
O1	0.85144 (15)	0.3722 (3)	0.64738 (14)	0.0239 (5)
C1	0.8416 (2)	0.4921 (3)	0.88344 (19)	0.0197 (6)
C2	0.8013 (2)	0.5688 (4)	0.8151 (2)	0.0286 (8)
H2A	0.7473	0.5313	0.8072	0.034*
H2B	0.7955	0.6658	0.8292	0.034*
C3	0.8470 (3)	0.5590 (4)	0.7396 (2)	0.0289 (8)
H3	0.9021	0.5935	0.7492	0.035*
C4	0.85370 (19)	0.4092 (3)	0.71536 (19)	0.0191 (6)
C4A	0.87029 (17)	0.3169 (3)	0.77841 (18)	0.0148 (6)
C5	0.91327 (18)	0.0866 (3)	0.7158 (2)	0.0194 (6)
H5	0.9066	0.1127	0.6633	0.023*
C5A	0.89776 (17)	0.1783 (3)	0.77599 (19)	0.0163 (6)
C6	0.9385 (2)	−0.0429 (3)	0.7349 (2)	0.0239 (7)
H6	0.9489	−0.1066	0.6948	0.029*
C7	0.9491 (2)	−0.0818 (3)	0.8121 (2)	0.0256 (7)
H7	0.9658	−0.1718	0.8234	0.031*
C8	0.9357 (2)	0.0079 (3)	0.8720 (2)	0.0224 (7)
H8	0.9437	−0.0184	0.9243	0.027*
C8A	0.90996 (18)	0.1386 (3)	0.85310 (19)	0.0170 (6)
N9	0.89088 (16)	0.2472 (3)	0.90098 (16)	0.0181 (5)
C9A	0.86652 (18)	0.3536 (3)	0.85548 (18)	0.0155 (6)
C10	0.8955 (2)	0.2417 (4)	0.9851 (2)	0.0235 (7)
H10A	0.9219	0.1574	1.0009	0.035*
H10B	0.8418	0.2445	1.0069	0.035*
H10C	0.9261	0.3197	1.0041	0.035*
C11	0.8106 (2)	0.6453 (4)	0.6759 (2)	0.0255 (7)
H11A	0.8438	0.6398	0.6294	0.038*
H11B	0.8074	0.7400	0.6932	0.038*
H11C	0.7571	0.6118	0.6641	0.038*
C12	0.8746 (3)	0.6719 (5)	0.9974 (3)	0.0377 (10)
H12A	0.9120	0.7095	1.0360	0.045*
H12B	0.8452	0.7481	0.9734	0.045*
C13	0.8179 (3)	0.5753 (5)	1.0353 (2)	0.0354 (9)
H13A	0.7806	0.6254	1.0692	0.043*
H13B	0.8474	0.5085	1.0671	0.043*

	U11	U22	U33	U12	U13	U23
S1	0.0233 (4)	0.0244 (4)	0.0275 (5)	−0.0063 (3)	0.0077 (3)	−0.0106 (3)
S2	0.0184 (4)	0.0257 (4)	0.0362 (5)	0.0007 (3)	0.0008 (3)	−0.0062 (4)
O1	0.0292 (12)	0.0296 (13)	0.0130 (12)	0.0025 (10)	−0.0008 (10)	0.0004 (9)
C1	0.0298 (16)	0.0154 (14)	0.0138 (15)	0.0006 (12)	−0.0039 (13)	−0.0015 (11)
C2	0.0336 (18)	0.0278 (18)	0.0243 (19)	0.0059 (15)	−0.0034 (15)	0.0004 (14)
C3	0.041 (2)	0.0244 (16)	0.0210 (18)	0.0081 (15)	−0.0011 (16)	0.0028 (14)
C4	0.0193 (14)	0.0248 (15)	0.0133 (15)	0.0020 (12)	−0.0002 (12)	0.0016 (12)
C4A	0.0144 (12)	0.0158 (13)	0.0142 (14)	−0.0020 (11)	0.0003 (11)	−0.0005 (11)
C5	0.0170 (13)	0.0209 (15)	0.0204 (16)	−0.0018 (12)	0.0045 (12)	−0.0032 (12)
C5A	0.0144 (13)	0.0169 (14)	0.0175 (15)	−0.0021 (11)	0.0031 (11)	−0.0002 (11)
C6	0.0209 (15)	0.0196 (15)	0.031 (2)	−0.0013 (12)	0.0068 (14)	−0.0083 (13)
C7	0.0216 (15)	0.0173 (14)	0.038 (2)	0.0013 (12)	0.0063 (14)	0.0014 (14)
C8	0.0207 (15)	0.0184 (15)	0.0279 (19)	0.0014 (12)	0.0019 (13)	0.0062 (13)
C8A	0.0163 (13)	0.0160 (14)	0.0187 (16)	−0.0011 (11)	0.0011 (12)	−0.0014 (12)
N9	0.0226 (12)	0.0173 (12)	0.0143 (13)	0.0013 (10)	0.0000 (11)	0.0017 (10)
C9A	0.0175 (13)	0.0155 (13)	0.0134 (15)	−0.0011 (11)	−0.0034 (11)	0.0012 (11)
C10	0.0287 (16)	0.0250 (16)	0.0167 (17)	0.0012 (14)	−0.0053 (13)	0.0050 (13)
C11	0.0318 (18)	0.0264 (16)	0.0184 (17)	0.0040 (14)	−0.0038 (14)	0.0076 (13)
C12	0.035 (2)	0.042 (2)	0.035 (2)	−0.0019 (18)	0.0037 (18)	−0.0165 (18)
C13	0.034 (2)	0.047 (2)	0.025 (2)	−0.0040 (18)	0.0074 (16)	−0.0127 (18)

S1—C1	1.823 (3)	C6—H6	0.9500
S1—C12	1.811 (4)	C7—H7	0.9500
S2—C1	1.847 (4)	C8—C7	1.379 (5)
S2—C13	1.824 (4)	C8—H8	0.9500
O1—C4	1.231 (4)	C8A—C8	1.396 (4)
C1—C2	1.558 (5)	N9—C8A	1.390 (4)
C1—C9A	1.505 (4)	N9—C9A	1.372 (4)
C2—H2A	0.9900	N9—C10	1.458 (4)
C2—H2B	0.9900	C9A—C4A	1.382 (4)
C3—C2	1.519 (5)	C10—H10A	0.9800
C3—C11	1.520 (5)	C10—H10B	0.9800
C3—H3	1.0000	C10—H10C	0.9800
C4—C3	1.536 (5)	C11—H11A	0.9800
C4A—C4	1.446 (4)	C11—H11B	0.9800
C4A—C5A	1.441 (4)	C11—H11C	0.9800
C5—C6	1.383 (5)	C12—C13	1.498 (6)
C5—H5	0.9500	C12—H12A	0.9900
C5A—C5	1.402 (4)	C12—H12B	0.9900
C5A—C8A	1.405 (5)	C13—H13A	0.9900
C6—C7	1.400 (6)	C13—H13B	0.9900
C12—S1—C1	96.24 (18)	C8—C7—H7	119.3
C13—S2—C1	98.43 (17)	C7—C8—C8A	117.7 (3)
S1—C1—S2	107.72 (17)	C7—C8—H8	121.2
C2—C1—S1	114.8 (2)	C8A—C8—H8	121.2
C2—C1—S2	103.4 (2)	C8—C8A—C5A	121.6 (3)
C9A—C1—S1	108.6 (2)	N9—C8A—C5A	108.5 (3)
C9A—C1—S2	114.0 (2)	N9—C8A—C8	129.9 (3)
C9A—C1—C2	108.4 (3)	C8A—N9—C10	123.6 (3)
C1—C2—H2A	108.8	C9A—N9—C8A	108.3 (3)
C1—C2—H2B	108.8	C9A—N9—C10	128.0 (3)
C3—C2—C1	113.6 (3)	C4A—C9A—C1	124.0 (3)
C3—C2—H2A	108.8	N9—C9A—C1	126.1 (3)
C3—C2—H2B	108.8	N9—C9A—C4A	109.9 (3)
H2A—C2—H2B	107.7	N9—C10—H10A	109.5
C2—C3—C11	112.5 (3)	N9—C10—H10B	109.5
C2—C3—C4	109.4 (3)	N9—C10—H10C	109.5
C2—C3—H3	107.7	H10A—C10—H10B	109.5
C4—C3—H3	107.7	H10A—C10—H10C	109.5
C11—C3—C4	111.6 (3)	H10B—C10—H10C	109.5
C11—C3—H3	107.7	C3—C11—H11A	109.5
O1—C4—C3	122.8 (3)	C3—C11—H11B	109.5
O1—C4—C4A	122.7 (3)	C3—C11—H11C	109.5
C4A—C4—C3	114.3 (3)	H11A—C11—H11B	109.5
C5A—C4A—C4	129.4 (3)	H11A—C11—H11C	109.5
C9A—C4A—C4	123.7 (3)	H11B—C11—H11C	109.5
C9A—C4A—C5A	106.8 (3)	S1—C12—H12A	110.3
C5A—C5—H5	120.9	S1—C12—H12B	110.3
C6—C5—C5A	118.3 (3)	C13—C12—S1	107.2 (3)
C6—C5—H5	120.9	C13—C12—H12A	110.3
C5—C5A—C4A	133.7 (3)	C13—C12—H12B	110.3
C5—C5A—C8A	119.9 (3)	H12A—C12—H12B	108.5
C8A—C5A—C4A	106.4 (3)	S2—C13—H13A	110.3
C5—C6—C7	121.2 (3)	S2—C13—H13B	110.3
C5—C6—H6	119.4	C12—C13—S2	107.3 (3)
C7—C6—H6	119.4	C12—C13—H13A	110.3
C6—C7—H7	119.3	C12—C13—H13B	110.3
C8—C7—C6	121.3 (3)	H13A—C13—H13B	108.5
C12—S1—C1—S2	−23.5 (2)	C4—C4A—C5A—C8A	175.7 (3)
C12—S1—C1—C2	91.1 (3)	C9A—C4A—C5A—C5	−180.0 (3)
C12—S1—C1—C9A	−147.4 (3)	C9A—C4A—C5A—C8A	−0.5 (3)
C1—S1—C12—C13	45.7 (3)	C5A—C5—C6—C7	−0.5 (5)
C13—S2—C1—S1	−0.1 (2)	C4A—C5A—C5—C6	−179.0 (3)
C13—S2—C1—C2	−122.0 (3)	C8A—C5A—C5—C6	1.6 (4)
C13—S2—C1—C9A	120.4 (3)	C4A—C5A—C8A—N9	0.1 (3)
C1—S2—C13—C12	30.4 (3)	C4A—C5A—C8A—C8	179.0 (3)
S1—C1—C2—C3	75.4 (4)	C5—C5A—C8A—N9	179.6 (3)
S2—C1—C2—C3	−167.6 (3)	C5—C5A—C8A—C8	−1.5 (5)
C9A—C1—C2—C3	−46.2 (4)	C5—C6—C7—C8	−0.8 (5)
S1—C1—C9A—N9	67.1 (4)	C8A—C8—C7—C6	1.0 (5)
S1—C1—C9A—C4A	−110.8 (3)	N9—C8A—C8—C7	178.8 (3)
S2—C1—C9A—N9	−53.0 (4)	C5A—C8A—C8—C7	0.2 (5)
S2—C1—C9A—C4A	129.1 (3)	C9A—N9—C8A—C5A	0.4 (3)
C2—C1—C9A—N9	−167.6 (3)	C9A—N9—C8A—C8	−178.4 (3)
C2—C1—C9A—C4A	14.5 (4)	C10—N9—C8A—C5A	179.2 (3)
C4—C3—C2—C1	60.7 (4)	C10—N9—C8A—C8	0.4 (5)
C11—C3—C2—C1	−174.7 (3)	C8A—N9—C9A—C1	−178.9 (3)
O1—C4—C3—C2	144.3 (3)	C8A—N9—C9A—C4A	−0.7 (4)
O1—C4—C3—C11	19.1 (5)	C10—N9—C9A—C1	2.4 (5)
C4A—C4—C3—C2	−41.2 (4)	C10—N9—C9A—C4A	−179.5 (3)
C4A—C4—C3—C11	−166.4 (3)	N9—C9A—C4A—C4	−175.7 (3)
C5A—C4A—C4—O1	10.0 (5)	N9—C9A—C4A—C5A	0.8 (3)
C5A—C4A—C4—C3	−164.4 (3)	C1—C9A—C4A—C4	2.5 (5)
C9A—C4A—C4—O1	−174.3 (3)	C1—C9A—C4A—C5A	179.0 (3)
C9A—C4A—C4—C3	11.2 (5)	S1—C12—C13—S2	−50.0 (4)
C4—C4A—C5A—C5	−3.8 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O1i	0.99	2.60	3.483 (5)	149
C2—H2A···Cg3ii	0.99	2.89	3.813 (4)	155

Table 1

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O1i	0.99	2.60	3.483 (5)	149
C2—H2A⋯Cg3ii	0.99	2.89	3.813 (4)	155

Symmetry codes: (i) ; (ii) .