3,3-Ethyl­enedithio-3,3a,4,5,10,10b-hexa­hydro-2H-furo[2,3-a]carbazole

Uludağ, N.; Öztürk, A.; Hökelek, T.; Erdoğan, Ü.I.

doi:10.1107/S1600536809006035

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages o595-o596

doi:10.1107/S1600536809006035

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3,3-Ethylenedithio-3,3a,4,5,10,10b-hexahydro-2H-furo[2,3-a]carbazole

Nesimi Uludağ,^a Aslı Öztürk,^b Tuncer Hökelek ^b and Ümit Işık Erdoğan ^c ^*

^aDepartment of Chemistry, Faculty of Technical Education, Mersin University, 33500 Mersin, Turkey, ^bDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and ^cDepartment of Chemistry Education, Faculty of Education, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 29 January 2009; accepted 19 February 2009; online 25 February 2009)

The title compound, C₁₆H₁₇NOS₂, consists of a carbazole skeleton with tetrahydrofuran and dithiolane rings. In the indole ring system, the benzene and pyrrole rings are nearly coplanar, forming a dihedral angle of 1.57 (15)°. The cyclohexenone and tetrahydrofuran rings have envelope conformations, while the dithiolane ring adopts a twist conformation. In the crystal structure, pairs of weak intermolecular N—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers with R₂²(16) ring motifs. Weak C—H⋯π interactions may further stabilize the structure.

Related literature

For general background, see: Phillipson & Zenk (1980 ); Saxton (1983 ); Abraham (1975 ). For related structures, see: Hökelek et al. (1994 , 1998 , 1999 , 2004 , 2006 ); Patır et al. (1997 ); Hökelek & Patır (1999 ,2002 ); Çaylak et al. (2007 ). For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 )

Experimental

Crystal data

C₁₆H₁₇NOS₂
M_r = 303.43
Orthorhombic, P b c n
a = 21.7617 (5) Å
b = 8.4992 (2) Å
c = 15.2115 (3) Å
V = 2813.47 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 294 K
0.35 × 0.20 × 0.15 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.913, T_max = 0.944
8196 measured reflections
2289 independent reflections
1105 reflections with I > 2σ(I)
R_int = 0.149
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 0.98
2289 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10⋯S2ⁱ	0.81 (4)	2.71 (4)	3.487 (4)	161 (4)
C3A—H3A⋯Cg2ⁱⁱ	0.98	2.85	3.725 (4)	149
C4—H4B⋯Cg1ⁱⁱⁱ	0.97	2.79	3.556 (5)	136
C5—H5A⋯Cg1ⁱⁱ	0.97	2.96	3.714 (5)	135
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y+2, -z; (iii) $[-x, y, -z+{\script{1\over 2}}]$ . Cg1 and Cg2 are centroids of the C5b/C6–C9/C9a and C5a/C5b/C9a/N10/C10a rings, respectively.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006035/xu2478sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006035/xu2478Isup2.hkl

checkCIF report

Comment top

Tetrahydrocarbazole systems are present in the framework of a number of indole-type alkaloids of biological interest (Phillipson & Zenk, 1980; Saxton, 1983; Abraham, 1975). The structures of tricyclic, tetracyclic and pentacyclic ring systems with dithiolane and other substituents of the tetrahydrocarbazole core, have been the subject of much interest in our laboratory. These include 1,2,3,4-tetrahydrocarbazole-1-spiro-2'-[1,3]dithiolane, (II) (Hökelek et al., 1994), N-(2-methoxyethyl)-N-{2,3,4,9-tetrahydrospiro[1H-carbazole-1, 2-(1,3)dithiolane]-4-yl}benzene-sulfonamide, (III) (Patır et al., 1997), spiro[carbazole-1(2H),2'-[1,3]-dithiolan]-4(3H)-one, (IV) (Hökelek et al., 1998), 9-acetonyl-3-ethylidene-1,2,3,4-tetrahydrospiro[carbazole-1,2'-[1,3] dithiolan]-4-one, (V) (Hökelek et al., 1999), N-(2,2-dimethoxyethyl)-N -{9-methoxymethyl-1,2,3,4-tetrahydrospiro[carbazole-1,2'-[1,3]dithiolan] -4-yl}benzamide, (VI) (Hökelek & Patır, 1999), 3a,4,10,10b-tetrahydro-2H -furo[2,3-a]carbazol-5(3H)-one, (VII) (Çaylak et al., 2007); also the pentacyclic compounds 6-ethyl-4-(2-methoxyethyl)-2,6-methano-5-oxo-hexahydro- pyrrolo(2,3 - d)carbazole-1-spiro-2'-(1,3)dithiolane, (VIII) (Hökelek & Patır, 2002), N-(2-benzyloxyethyl)-4,7-dimethyl-6-(1,3-dithiolan-2-yl)-1,2, 3,4,5,6-hexahydro-1,5-methano-2-azocino[4,3-b]indol-2-one, (IX) (Hökelek et al., 2004) and 4-ethyl-6,6-ethylenedithio-2-(2-methoxyethyl)-7-methoxy- methylene-2,3,4,5,6,7-hexahydro-1,5-methano-1H-azocino[4,3-b]indol-3-one, (X) (Hökelek et al., 2006). The title compound, (I), may be considered as a synthetic precursor of tetracyclic indole alkaloids of biological interests. The present study was undertaken to ascertain its crystal structure.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. It consists of a carbazole skeleton with tetrahydrofuran and dithiolane rings. The bonds N10—C9a [1.378 (5) Å] and N10—C10a [1.371 (5) Å] generally agree with those in compounds (II)-(X). In all structures atom N10 is substituted.

An examination of the deviations from the least-squares planes through individual rings shows that rings A (C5b/C6—C9/C9a) and B (C5a/C5b/C9a/N10/C10a) are planar. They are also nearly coplanar with a dihedral angle of A/B = 1.57 (15)°. Rings C (C3a/C4/C5/C5a/C10a/C10b), D (O1/C2/C3/C3a/C10b) and E (S1/S2/C3/C11/C12) are not planar. Rings C and D have envelope conformations with atoms C4 and C3 displaced by -0.677 (4) Å (for ring C) and 0.568 (4) Å (for ring D) from the planes of the other ring atoms, respectively. Ring E adopts twisted conformation. Rings C and D have pseudo mirror planes running through atoms C10a and C4 (for ring C) and running through atom C3 and midpoint of O1—C10b bond (for ring D), as can be deduced from the torsion angles (Table 1).

In the crystal structure, intermolecular N—H···S hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers (Fig. 2) by forming the R₂²(16) ring motifs (Bernstein et al., 1995), in which they may be effective in the stabilization of the structure. The weak C—H···π interactions (Table 1) may further stabilize the structure.

Related literature top

For general background, see: Phillipson & Zenk (1980); Saxton (1983); Abraham (1975). For related structures, see: Hökelek et al. (1994, 1998, 1999, 2004, 2006); Patır et al. (1997); Hökelek & Patır (1999,2002); Çaylak et al. (2007). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). Cg1 and Cg2 are centroids of the C5b/C6–C9/C9a and C5a/C5b/C9a/N10/C10a rings, respectively.

Experimental top

For the preparation of the title compound, (I), sodium borohydride (5.00 g, 132.00 mmol) was added to a solution of ethyl 2-(1-oxo-2,3,4,9-tetrahydro-1H -carbazol-2yl)-1,3-dithiolane-2-carboxylate (5.00 g, 13.83 mmol) in THF (50 ml), and stirred at room temperature for 3 h. Then, the reaction mixture was poured into HCl (15%, 100 ml). The crude product was filtered and recrystallized from acetone (yield; 3.2 g, 77%, m.p. 468 K).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

3,3-Ethylenedithio-3,3a,4,5,10,10b-hexahydro-2H- furo[2,3-a]carbazole top

Crystal data top

C₁₆H₁₇NOS₂	F(000) = 1280
M_r = 303.43	D_x = 1.433 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 25 reflections
a = 21.7617 (5) Å	θ = 9.3–16.7°
b = 8.4992 (2) Å	µ = 0.37 mm⁻¹
c = 15.2115 (3) Å	T = 294 K
V = 2813.47 (11) Å³	Prism, colorless
Z = 8	0.35 × 0.20 × 0.15 mm

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	1105 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.149
Graphite monochromator	θ_max = 24.3°, θ_min = 2.6°
Non–profiled ω scans	h = −25→25
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
T_min = 0.913, T_max = 0.944	l = −17→0
8196 measured reflections	3 standard reflections every 120 min
2289 independent reflections	intensity decay: 1%

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0328P)² + 1.8766P] where P = (F_o² + 2F_c²)/3
2289 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₆H₁₇NOS₂	V = 2813.47 (11) Å³
M_r = 303.43	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 21.7617 (5) Å	µ = 0.37 mm⁻¹
b = 8.4992 (2) Å	T = 294 K
c = 15.2115 (3) Å	0.35 × 0.20 × 0.15 mm

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	1105 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.149
T_min = 0.913, T_max = 0.944	3 standard reflections every 120 min
8196 measured reflections	intensity decay: 1%
2289 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.24 e Å⁻³
2289 reflections	Δρ_min = −0.23 e Å⁻³
185 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
S1	0.32178 (5)	0.10773 (14)	0.23756 (8)	0.0538 (4)
S2	0.33505 (5)	−0.00621 (14)	0.05706 (9)	0.0538 (3)
O1	0.48005 (12)	0.0372 (3)	0.1141 (2)	0.0597 (9)
C2	0.43301 (17)	−0.0004 (5)	0.1754 (3)	0.0499 (12)
H2A	0.4450	0.0310	0.2343	0.060*
H2B	0.4250	−0.1126	0.1753	0.060*
C3	0.37602 (18)	0.0902 (5)	0.1461 (3)	0.0394 (11)
C3A	0.40456 (17)	0.2447 (4)	0.1109 (3)	0.0391 (11)
H3A	0.3786	0.2865	0.0637	0.047*
C4	0.41256 (17)	0.3698 (4)	0.1817 (3)	0.0402 (11)
H4A	0.3724	0.4058	0.2008	0.048*
H4B	0.4332	0.3238	0.2320	0.048*
C5	0.44962 (17)	0.5095 (5)	0.1485 (3)	0.0423 (11)
H5A	0.4272	0.5632	0.1023	0.051*
H5B	0.4566	0.5834	0.1961	0.051*
C5A	0.50957 (18)	0.4512 (4)	0.1140 (3)	0.0375 (10)
C5B	0.56863 (19)	0.5223 (5)	0.1102 (3)	0.0402 (11)
C6	0.5923 (2)	0.6705 (5)	0.1333 (3)	0.0487 (12)
H6	0.5664	0.7483	0.1552	0.058*
C7	0.6542 (2)	0.6994 (6)	0.1233 (3)	0.0582 (14)
H7	0.6700	0.7973	0.1384	0.070*
C8	0.6930 (2)	0.5844 (7)	0.0909 (3)	0.0608 (14)
H8	0.7347	0.6070	0.0850	0.073*
C9	0.6721 (2)	0.4373 (5)	0.0671 (3)	0.0562 (13)
H9	0.6985	0.3607	0.0454	0.067*
C9A	0.60977 (19)	0.4090 (5)	0.0771 (3)	0.0426 (11)
C10A	0.51613 (17)	0.3010 (5)	0.0837 (3)	0.0365 (11)
C10B	0.46569 (17)	0.1854 (4)	0.0715 (3)	0.0401 (11)
H10B	0.4600	0.1667	0.0085	0.048*
N10	0.57621 (16)	0.2746 (5)	0.0610 (3)	0.0469 (10)
H10	0.5901 (17)	0.196 (4)	0.038 (3)	0.043 (15)*
C11	0.2649 (2)	−0.0299 (5)	0.1985 (3)	0.0658 (14)
H11A	0.2507	−0.0947	0.2469	0.079*
H11B	0.2299	0.0269	0.1750	0.079*
C12	0.2921 (2)	−0.1318 (5)	0.1286 (3)	0.0646 (14)
H12A	0.2599	−0.1851	0.0961	0.078*
H12B	0.3188	−0.2106	0.1545	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0516 (7)	0.0527 (7)	0.0570 (8)	−0.0052 (6)	0.0097 (7)	−0.0042 (7)
S2	0.0541 (7)	0.0516 (7)	0.0558 (7)	−0.0125 (7)	−0.0012 (6)	−0.0103 (7)
O1	0.0462 (19)	0.040 (2)	0.093 (3)	0.0094 (14)	0.0183 (18)	0.0122 (18)
C2	0.042 (2)	0.042 (2)	0.065 (3)	0.001 (2)	0.001 (2)	0.008 (3)
C3	0.039 (3)	0.036 (2)	0.042 (3)	−0.003 (2)	−0.001 (2)	−0.001 (2)
C3A	0.038 (2)	0.035 (2)	0.045 (3)	0.0018 (19)	−0.002 (2)	0.000 (2)
C4	0.034 (2)	0.041 (3)	0.047 (3)	0.000 (2)	0.004 (2)	−0.007 (2)
C5	0.048 (3)	0.036 (2)	0.043 (3)	0.001 (2)	−0.001 (2)	−0.004 (2)
C5A	0.040 (3)	0.040 (3)	0.033 (3)	0.000 (2)	0.002 (2)	−0.001 (2)
C5B	0.050 (3)	0.042 (3)	0.029 (2)	−0.003 (2)	−0.001 (2)	0.001 (2)
C6	0.059 (3)	0.049 (3)	0.038 (3)	−0.005 (2)	0.002 (2)	0.002 (2)
C7	0.067 (3)	0.061 (3)	0.046 (3)	−0.025 (3)	−0.002 (3)	0.006 (3)
C8	0.047 (3)	0.082 (4)	0.054 (3)	−0.017 (3)	0.000 (2)	0.009 (3)
C9	0.049 (3)	0.059 (3)	0.061 (3)	−0.003 (3)	0.007 (3)	0.005 (3)
C9A	0.044 (3)	0.046 (3)	0.038 (3)	−0.007 (2)	−0.001 (2)	0.003 (2)
C10A	0.034 (3)	0.040 (3)	0.036 (3)	0.002 (2)	−0.002 (2)	0.002 (2)
C10B	0.042 (3)	0.034 (2)	0.045 (3)	−0.004 (2)	0.004 (2)	0.000 (2)
N10	0.042 (2)	0.040 (2)	0.059 (3)	0.004 (2)	0.011 (2)	−0.006 (2)
C11	0.051 (3)	0.066 (4)	0.080 (4)	−0.017 (3)	0.005 (3)	0.002 (3)
C12	0.070 (3)	0.048 (3)	0.076 (4)	−0.020 (3)	0.004 (3)	−0.007 (3)

Geometric parameters (Å, º) top

S1—C3	1.830 (4)	C5B—C6	1.405 (5)
S1—C11	1.803 (4)	C6—H6	0.9300
S2—C3	1.817 (4)	C7—C6	1.377 (5)
S2—C12	1.788 (4)	C7—C8	1.383 (6)
O1—C2	1.421 (5)	C7—H7	0.9300
O1—C10B	1.450 (4)	C8—H8	0.9300
C2—H2A	0.9700	C9—C8	1.379 (6)
C2—H2B	0.9700	C9—H9	0.9300
C3—C2	1.526 (5)	C9A—C9	1.385 (5)
C3A—C3	1.548 (5)	C9A—C5B	1.408 (5)
C3A—C4	1.523 (5)	C10A—C10B	1.485 (5)
C3A—C10B	1.544 (5)	C10B—H10B	0.9800
C3A—H3A	0.9800	N10—C10A	1.371 (5)
C4—C5	1.522 (5)	N10—C9A	1.378 (5)
C4—H4A	0.9700	N10—H10	0.81 (3)
C4—H4B	0.9700	C11—H11A	0.9700
C5—H5A	0.9700	C11—H11B	0.9700
C5—H5B	0.9700	C12—C11	1.495 (6)
C5A—C5	1.491 (5)	C12—H12A	0.9700
C5A—C10A	1.365 (5)	C12—H12B	0.9700
C5B—C5A	1.421 (5)

C11—S1—C3	98.0 (2)	C5B—C6—H6	120.3
C12—S2—C3	94.1 (2)	C7—C6—C5B	119.3 (4)
C2—O1—C10B	109.5 (3)	C7—C6—H6	120.3
O1—C2—C3	106.3 (3)	C6—C7—C8	120.8 (4)
O1—C2—H2A	110.5	C6—C7—H7	119.6
O1—C2—H2B	110.5	C8—C7—H7	119.6
C3—C2—H2A	110.5	C9—C8—C7	122.1 (4)
C3—C2—H2B	110.5	C9—C8—H8	119.0
H2A—C2—H2B	108.7	C7—C8—H8	119.0
S2—C3—S1	106.7 (2)	C8—C9—C9A	116.9 (4)
C2—C3—S1	110.1 (3)	C8—C9—H9	121.5
C2—C3—S2	112.9 (3)	C9A—C9—H9	121.5
C2—C3—C3A	101.7 (3)	C9—C9A—C5B	122.9 (4)
C3A—C3—S1	116.9 (3)	N10—C9A—C9	130.1 (4)
C3A—C3—S2	108.7 (3)	N10—C9A—C5B	107.1 (4)
C3—C3A—H3A	109.3	O1—C10B—C3A	107.2 (3)
C4—C3A—C3	113.2 (3)	O1—C10B—C10A	111.1 (3)
C4—C3A—H3A	109.3	O1—C10B—H10B	108.9
C4—C3A—C10B	113.8 (3)	N10—C10A—C10B	124.4 (4)
C10B—C3A—C3	101.7 (3)	C3A—C10B—H10B	108.9
C10B—C3A—H3A	109.3	C5A—C10A—N10	109.8 (4)
C3A—C4—H4A	109.3	C5A—C10A—C10B	125.7 (4)
C3A—C4—H4B	109.3	C10A—C10B—C3A	111.9 (3)
C5—C4—C3A	111.8 (3)	C10A—C10B—H10B	108.9
C5—C4—H4A	109.3	C9A—N10—H10	124 (3)
C5—C4—H4B	109.3	C10A—N10—C9A	109.0 (4)
H4A—C4—H4B	107.9	C10A—N10—H10	127 (3)
C4—C5—H5A	109.9	S1—C11—H11A	109.7
C4—C5—H5B	109.9	S1—C11—H11B	109.7
C5A—C5—C4	108.7 (3)	C12—C11—S1	109.8 (3)
C5A—C5—H5A	109.9	C12—C11—H11A	109.7
C5A—C5—H5B	109.9	C12—C11—H11B	109.7
H5A—C5—H5B	108.3	H11A—C11—H11B	108.2
C5B—C5A—C5	131.6 (4)	S2—C12—H12A	110.3
C10A—C5A—C5	121.4 (4)	S2—C12—H12B	110.3
C10A—C5A—C5B	106.8 (4)	C11—C12—S2	107.1 (3)
C6—C5B—C5A	134.6 (4)	C11—C12—H12A	110.3
C6—C5B—C9A	118.0 (4)	C11—C12—H12B	110.3
C9A—C5B—C5A	107.4 (4)	H12A—C12—H12B	108.6

C11—S1—C3—S2	15.4 (3)	C5A—C5B—C6—C7	177.8 (4)
C11—S1—C3—C2	−107.4 (3)	C9A—C5B—C6—C7	−0.2 (6)
C11—S1—C3—C3A	137.2 (3)	C5—C5A—C10A—N10	−176.3 (4)
C3—S1—C11—C12	17.0 (4)	C5—C5A—C10A—C10B	7.2 (6)
C12—S2—C3—S1	−36.2 (2)	C5B—C5A—C10A—N10	−0.1 (5)
C12—S2—C3—C2	84.9 (3)	C5B—C5A—C10A—C10B	−176.6 (4)
C12—S2—C3—C3A	−163.1 (3)	C6—C5B—C5A—C5	−2.7 (8)
C3—S2—C12—C11	49.5 (4)	C6—C5B—C5A—C10A	−178.4 (5)
C10B—O1—C2—C3	22.4 (4)	C9A—C5B—C5A—C5	175.4 (4)
C2—O1—C10B—C3A	0.5 (4)	C9A—C5B—C5A—C10A	−0.2 (4)
C2—O1—C10B—C10A	123.0 (4)	C8—C7—C6—C5B	−0.1 (7)
C4—C3A—C3—S1	31.6 (4)	C6—C7—C8—C9	0.2 (7)
C4—C3A—C3—S2	152.4 (3)	C9A—C9—C8—C7	0.0 (7)
C4—C3A—C3—C2	−88.3 (4)	N10—C9A—C5B—C5A	0.5 (4)
C10B—C3A—C3—S1	154.1 (3)	N10—C9A—C5B—C6	179.0 (4)
C10B—C3A—C3—S2	−85.1 (3)	C9—C9A—C5B—C5A	−178.1 (4)
C10B—C3A—C3—C2	34.2 (4)	C9—C9A—C5B—C6	0.4 (6)
C3—C3A—C4—C5	171.0 (3)	N10—C9A—C9—C8	−178.5 (4)
C10B—C3A—C4—C5	55.6 (4)	C5B—C9A—C9—C8	−0.3 (6)
C4—C3A—C10B—O1	99.6 (4)	N10—C10A—C10B—O1	55.3 (5)
C3—C3A—C10B—O1	−22.4 (4)	N10—C10A—C10B—C3A	175.1 (4)
C4—C3A—C10B—C10A	−22.4 (5)	C5A—C10A—C10B—O1	−128.7 (4)
C3—C3A—C10B—C10A	−144.4 (3)	C5A—C10A—C10B—C3A	−9.0 (6)
S1—C3—C2—O1	−160.3 (3)	C9A—N10—C10A—C5A	0.4 (5)
S2—C3—C2—O1	80.6 (4)	C9A—N10—C10A—C10B	176.9 (4)
C3A—C3—C2—O1	−35.7 (4)	C10A—N10—C9A—C5B	−0.5 (5)
C3A—C4—C5—C5A	−55.3 (4)	C10A—N10—C9A—C9	177.8 (4)
C5B—C5A—C5—C4	−149.7 (4)	S2—C12—C11—S1	−44.2 (4)
C10A—C5A—C5—C4	25.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···S2ⁱ	0.81 (4)	2.71 (4)	3.487 (4)	161 (4)
C3A—H3A···Cg2ⁱⁱ	0.98	2.85	3.725 (4)	149
C4—H4B···Cg1ⁱⁱⁱ	0.97	2.79	3.556 (5)	136
C5—H5A···Cg1ⁱⁱ	0.97	2.96	3.714 (5)	135

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₇NOS₂
M_r	303.43
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	294
a, b, c (Å)	21.7617 (5), 8.4992 (2), 15.2115 (3)
V (Å³)	2813.47 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.35 × 0.20 × 0.15

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.913, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	8196, 2289, 1105
R_int	0.149
(sin θ/λ)_max (Å⁻¹)	0.579

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 0.98
No. of reflections	2289
No. of parameters	185
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.23

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected torsion angles (º) top

C10B—O1—C2—C3	22.4 (4)	C3A—C3—C2—O1	−35.7 (4)
C2—O1—C10B—C3A	0.5 (4)	C3A—C4—C5—C5A	−55.3 (4)
C10B—C3A—C3—C2	34.2 (4)	C10A—C5A—C5—C4	25.4 (5)
C10B—C3A—C4—C5	55.6 (4)	C5—C5A—C10A—C10B	7.2 (6)
C3—C3A—C10B—O1	−22.4 (4)	C5A—C10A—C10B—C3A	−9.0 (6)
C4—C3A—C10B—C10A	−22.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···S2ⁱ	0.81 (4)	2.71 (4)	3.487 (4)	161 (4)
C3A—H3A···Cg2ⁱⁱ	0.98	2.85	3.725 (4)	149
C4—H4B···Cg1ⁱⁱⁱ	0.97	2.79	3.556 (5)	136
C5—H5A···Cg1ⁱⁱ	0.97	2.96	3.714 (5)	135

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

Acknowledgements

The authors acknowledge the purchase of the CAD-4 diffractometer under grant DPT/TBAG1 of the Scientific and Technical Research Council of Turkey.

References

Abraham, D. J. (1975). The Catharanthus Alkaloids, edited by W. I. Taylor & N. R. Fransworth, ch. 7 and 8. New York: Marcel Decker. Google Scholar
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
Bernstein, J., Davies, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Çaylak, N., Hökelek, T., Uludağ, N. & Patır, S. (2007). Acta Cryst. E63, o3913–o3914. Web of Science CSD CrossRef IUCr Journals Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. 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
Hökelek, T. & Patir, S. (1999). Acta Cryst. C55, 675–677. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T. & Patır, S. (2002). Acta Cryst. E58, o374–o376. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Patır, S., Gülce, A. & Okay, G. (1994). Acta Cryst. C50, 450–453. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T., Patir, S. & Uludauğ, N. (1999). Acta Cryst. C55, 114–116. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Uludağ, N. & Patır, S. (2004). Acta Cryst. E60, o25–o27. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Uludağ, N. & Patır, S. (2006). Acta Cryst. E62, o791–o793. Web of Science CSD CrossRef IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Patır, S., Okay, G., Gülce, A., Salih, B. & Hökelek, T. (1997). J. Heterocycl. Chem. 34, 1239–1242. CAS Google Scholar
Phillipson, J. D. & Zenk, M. H. (1980). Indole and Biogenetically Related Alkaloids, ch 3. New York: Academic Press. Google Scholar
Saxton, J. E. (1983). Editor. Heterocyclic Compounds, Vol. 25, The Monoterpenoid Indole Alkaloids, ch 8 and 11. New York: Wiley. 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