1,2-Dihydro-9H-carbazole-4(3H)-thione

W Adam Phelan; Maria Ngu-Schwemlein; Frank R Fronczek; Mark L McLaughlin; Steven F Watkins

doi:10.1107/S1600536811006623

. 2011 Mar 2;67(Pt 4):o757. doi: 10.1107/S1600536811006623

1,2-Dihydro-9H-carbazole-4(3H)-thione

W Adam Phelan ^a, Maria Ngu-Schwemlein ^a,^‡, Frank R Fronczek ^a,^*, Mark L McLaughlin ^a,^§, Steven F Watkins ^a

PMCID: PMC3099987 PMID: 21754054

Abstract

The crystal structure of the title compound, C₁₂H₁₁NS, features parallel chains of alternating N—H⋯S hydrogen-bonded mirror-image conformers along [10 Inline graphic ]. The molecular conformation is that of an envelope, with all of the framework atoms except one close to a mean plane (rms deviation 0.054 Å); one C atom of the cyclohexenethione ring forms the envelope flap, which makes a dihedral angle of 48.6 (1)° with the rest of the molecule. There is a π–π* interaction between pairs of enantiomers in adjacent chains; the distance between parallel planes is 3.466 (1) Å.

Related literature

For related structures, see: Hökelek et al. (1998 ▶); Ianelli et al. (1994 ▶); Çaylak et al. (2007 ▶); Rodriguez et al. (1989 ▶). Hückel calculations were performed using Chem3DPro (Cambridgesoft, 2009 ▶).

Experimental

Crystal data

C₁₂H₁₁NS
M _r = 201.28
Monoclinic,
a = 8.6353 (14) Å
b = 12.1395 (15) Å
c = 9.5808 (14) Å
β = 104.599 (10)°
V = 971.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 90 K
0.38 × 0.33 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.900, T _max = 0.958
6145 measured reflections
3305 independent reflections
2915 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.087
S = 1.04
3305 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006623/fl2336sup1.cif

e-67-0o757-sup1.cif^{(15.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006623/fl2336Isup2.hkl

e-67-0o757-Isup2.hkl^{(158.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯S1ⁱ	0.88	2.45	3.3187 (9)	172

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Symmetry code: (i) Inline graphic .

Acknowledgments

The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

The title compound (1, Fig.1) is the sulfur analog of substituted carbazole 1,2,3-trihydrocarbazol-4(9H)-one (2) (Rodriguez et al., 1989). Both 1 and 2 show the same molecular conformation (envelope, with flap angles 48.6 (1)° for 1 and 48.2 (1)° for 2) and similar H-bonded chains (Table 1) of alternating enantiomers (N···S = 3.319 (1) Å, N—H···S = 172.0 (1)°, and N···S═C = 98.0 (1)° for 1, N···O = 2.829 (1) Å, N—H···O = 162.3 (1)° and H···O═C = 117.5 (1)° for 2).

In 1, all H-bonded chains are parallel, extending along the [101] crystallographic direction, and adjacent chains 5.583 (1) Å apart are arranged in corrugated sheets parallel to the (010) crystallographic plane (Fig. 22)). The mean planes of adjacent sheets are 5.099 (1) Å apart, but enantiomers in adjacent sheets have parallel π-nodal planes and are only 3.466 (1) Å apart, indicative of a π-π* interaction. Extended Hückel calculations (Chem3DPro, Cambridgesoft, 2009) suggest that the π-HOMO and π*-LUMO orbitals in 1 are larger and closer in energy than those in 2. This may explain why molecules of 2 show no π-type interaction and are thus packed in a different pattern: H-bonded chains 5.359 (1) Å apart extend along the [011] and [011] directions in alternating sheets, so adjacent sheets are rotated by 76.5 (1)°. The distance between adjacent sheets is 4.979 (1) Å and the only interactions between them are C—H···C van der Waals and C—H···O contacts.

Experimental

A solution of 1,2-dihydrocarbazol-4(3H)-one (5.4 mmol) in anhydrous 1,2-dimethoxyethane (30 ml) was stirred at room temperature for 15 min. Upon dissolution, the solution was chilled in an ice-water bath. Lawesson reagent, 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, (2.9 mmol) was added to the vigorously stirred cold solution. The resulting mixture was stirred for 5 min and then allowed to warm to room temperature. After stirring for an additional 10 min, the white suspension dissolved, and the reaction mixture turned deep orange. The reaction mixture was poured into 150 ml of chilled water and the orange suspension was extracted with CHCl₃ (3 x 80 ml). Evaporation under reduced pressure left a deep orange residue, which was purified on a silica column (100 g). The orange band was eluted with ethyl acetate. Evaporation of the solvent in vacuo gave the title compound as a yellow powder (92%). Recrystallization from dichloromethane yielded yellow needles, m.p. 173–175°C.