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

Phelan, W.A.; Ngu-Schwemlein, M.; Fronczek, F.R.; McLaughlin, M.L.; Watkins, S.F.

doi:10.1107/S1600536811006623

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o757

doi:10.1107/S1600536811006623

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

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

^aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 24 January 2011; accepted 21 February 2011; online 2 March 2011)

The crystal structure of the title compound, C₁₂H₁₁NS, features parallel chains of alternating N—H⋯S hydrogen-bonded mirror-image conformers along [10 $[\overline{1}]$ ]. 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, P 2₁ /n
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[F² > 2σ(F²)] = 0.033
wR(F²) = 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

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
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

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

Figures top

	Fig. 1. View of 1 (50% probability displacement ellipsoids).
	Fig. 2. The unit cell, illustrating hydrogen bonds.

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

Crystal data top

C₁₂H₁₁NS	F(000) = 424
M_r = 201.28	D_x = 1.376 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 447(1) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.6353 (14) Å	Cell parameters from 3145 reflections
b = 12.1395 (15) Å	θ = 2.8–31.8°
c = 9.5808 (14) Å	µ = 0.29 mm⁻¹
β = 104.599 (10)°	T = 90 K
V = 971.9 (2) Å³	Prism, yellow
Z = 4	0.38 × 0.33 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	2915 reflections with I > 2σ(I)
ω and ϕ scans	R_int = 0.018
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	θ_max = 31.8°, θ_min = 2.8°
T_min = 0.900, T_max = 0.958	h = −12→12
6145 measured reflections	k = −17→15
3305 independent reflections	l = −14→14

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0381P)² + 0.4607P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.033	(Δ/σ)_max = 0.001
wR(F²) = 0.087	Δρ_max = 0.42 e Å⁻³
S = 1.04	Δρ_min = −0.30 e Å⁻³
3305 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
128 parameters	Extinction coefficient: 0.007 (2)
0 restraints

Crystal data top

C₁₂H₁₁NS	V = 971.9 (2) Å³
M_r = 201.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.6353 (14) Å	µ = 0.29 mm⁻¹
b = 12.1395 (15) Å	T = 90 K
c = 9.5808 (14) Å	0.38 × 0.33 × 0.15 mm
β = 104.599 (10)°

Data collection top

Nonius KappaCCD diffractometer	3305 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	2915 reflections with I > 2σ(I)
T_min = 0.900, T_max = 0.958	R_int = 0.018
6145 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	Δρ_max = 0.42 e Å⁻³
3305 reflections	Δρ_min = −0.30 e Å⁻³
128 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.

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

	x	y	z	U_iso*/U_eq
S1	0.73572 (3)	0.09251 (2)	0.17793 (3)	0.01632 (8)
N9	0.40190 (10)	0.23264 (7)	0.49231 (9)	0.01459 (16)
H9	0.3596	0.2739	0.5486	0.018*
C1	0.64126 (13)	0.35282 (8)	0.50486 (11)	0.01640 (19)
H1A	0.6442	0.3693	0.6067	0.02*
H1B	0.5975	0.4178	0.4456	0.02*
C2	0.81014 (12)	0.32729 (9)	0.49014 (11)	0.01613 (19)
H2A	0.8612	0.2724	0.5639	0.019*
H2B	0.8756	0.3953	0.5072	0.019*
C3	0.80512 (12)	0.28219 (8)	0.33970 (11)	0.01504 (18)
H3A	0.766	0.3409	0.2677	0.018*
H3B	0.9153	0.2631	0.3355	0.018*
C4	0.69952 (12)	0.18152 (8)	0.29869 (10)	0.01239 (17)
C5	0.40380 (12)	−0.00895 (8)	0.27655 (10)	0.01451 (18)
H5	0.4724	−0.0398	0.2234	0.017*
C6	0.26491 (13)	−0.06343 (9)	0.28577 (11)	0.0179 (2)
H6	0.2394	−0.1325	0.2389	0.021*
C7	0.16174 (13)	−0.01841 (9)	0.36297 (12)	0.0196 (2)
H7	0.0665	−0.0567	0.3655	0.024*
C8	0.19647 (13)	0.08102 (9)	0.43570 (11)	0.0181 (2)
H8	0.1273	0.1116	0.4885	0.022*
C10	0.53890 (12)	0.25494 (8)	0.45510 (10)	0.01313 (17)
C11	0.56930 (11)	0.17216 (8)	0.36283 (10)	0.01191 (17)
C12	0.44039 (11)	0.09230 (8)	0.34726 (10)	0.01234 (17)
C13	0.33703 (12)	0.13394 (8)	0.42784 (10)	0.01382 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01819 (13)	0.01449 (12)	0.01981 (13)	−0.00184 (8)	0.01132 (9)	−0.00327 (8)
N9	0.0156 (4)	0.0158 (4)	0.0144 (4)	0.0018 (3)	0.0077 (3)	−0.0002 (3)
C1	0.0194 (5)	0.0149 (4)	0.0159 (4)	−0.0014 (4)	0.0063 (4)	−0.0029 (3)
C2	0.0162 (4)	0.0168 (4)	0.0150 (4)	−0.0032 (4)	0.0031 (3)	−0.0016 (3)
C3	0.0149 (4)	0.0145 (4)	0.0167 (4)	−0.0031 (3)	0.0059 (3)	−0.0012 (3)
C4	0.0128 (4)	0.0125 (4)	0.0123 (4)	0.0008 (3)	0.0041 (3)	0.0011 (3)
C5	0.0149 (4)	0.0145 (4)	0.0141 (4)	−0.0005 (3)	0.0035 (3)	0.0017 (3)
C6	0.0182 (5)	0.0169 (5)	0.0175 (4)	−0.0039 (4)	0.0027 (4)	0.0026 (4)
C7	0.0156 (5)	0.0230 (5)	0.0204 (5)	−0.0045 (4)	0.0049 (4)	0.0056 (4)
C8	0.0140 (4)	0.0235 (5)	0.0182 (4)	0.0001 (4)	0.0068 (4)	0.0046 (4)
C10	0.0140 (4)	0.0142 (4)	0.0115 (4)	0.0012 (3)	0.0039 (3)	0.0012 (3)
C11	0.0120 (4)	0.0126 (4)	0.0115 (4)	0.0001 (3)	0.0037 (3)	0.0005 (3)
C12	0.0117 (4)	0.0142 (4)	0.0115 (4)	0.0006 (3)	0.0035 (3)	0.0026 (3)
C13	0.0136 (4)	0.0160 (4)	0.0126 (4)	0.0011 (3)	0.0046 (3)	0.0026 (3)

Geometric parameters (Å, º) top

C1—C10	1.4860 (14)	C5—H5	0.95
C1—C2	1.5318 (14)	C6—C7	1.4042 (16)
C1—H1A	0.99	C6—H6	0.95
C1—H1B	0.99	C7—C8	1.3882 (16)
C2—C3	1.5322 (14)	C7—H7	0.95
C2—H2A	0.99	C8—C13	1.3920 (14)
C2—H2B	0.99	C8—H8	0.95
C3—C4	1.5162 (14)	C10—N9	1.3463 (12)
C3—H3A	0.99	C10—C11	1.4061 (13)
C3—H3B	0.99	C11—C12	1.4553 (13)
C4—C11	1.4154 (13)	C12—C13	1.4127 (13)
C4—S1	1.6692 (10)	C13—N9	1.3988 (13)
C5—C6	1.3917 (14)	N9—H9	0.88
C5—C12	1.4006 (13)

C10—C1—C2	108.17 (8)	C5—C6—C7	121.32 (10)
C10—C1—H1A	110.1	C5—C6—H6	119.3
C2—C1—H1A	110.1	C7—C6—H6	119.3
C10—C1—H1B	110.1	C8—C7—C6	121.15 (10)
C2—C1—H1B	110.1	C8—C7—H7	119.4
H1A—C1—H1B	108.4	C6—C7—H7	119.4
C1—C2—C3	110.92 (8)	C7—C8—C13	117.08 (10)
C1—C2—H2A	109.5	C7—C8—H8	121.5
C3—C2—H2A	109.5	C13—C8—H8	121.5
C1—C2—H2B	109.5	N9—C10—C11	109.79 (9)
C3—C2—H2B	109.5	N9—C10—C1	124.55 (9)
H2A—C2—H2B	108	C11—C10—C1	125.66 (9)
C4—C3—C2	113.85 (8)	C10—C11—C4	120.68 (9)
C4—C3—H3A	108.8	C10—C11—C12	106.34 (8)
C2—C3—H3A	108.8	C4—C11—C12	132.83 (9)
C4—C3—H3B	108.8	C5—C12—C13	118.80 (9)
C2—C3—H3B	108.8	C5—C12—C11	135.05 (9)
H3A—C3—H3B	107.7	C13—C12—C11	106.14 (8)
C11—C4—C3	116.35 (8)	C8—C13—N9	128.98 (9)
C11—C4—S1	123.85 (7)	C8—C13—C12	122.96 (10)
C3—C4—S1	119.73 (7)	N9—C13—C12	108.06 (8)
C6—C5—C12	118.64 (9)	C10—N9—C13	109.64 (8)
C6—C5—H5	120.7	C10—N9—H9	125.2
C12—C5—H5	120.7	C13—N9—H9	125.2

C10—C1—C2—C3	49.84 (11)	C6—C5—C12—C13	1.45 (14)
C1—C2—C3—C4	−55.67 (11)	C6—C5—C12—C11	−179.79 (10)
C2—C3—C4—C11	28.23 (12)	C10—C11—C12—C5	−177.03 (10)
C2—C3—C4—S1	−154.52 (8)	C4—C11—C12—C5	7.46 (19)
C12—C5—C6—C7	0.52 (15)	C10—C11—C12—C13	1.84 (10)
C5—C6—C7—C8	−1.47 (16)	C4—C11—C12—C13	−173.67 (10)
C6—C7—C8—C13	0.35 (15)	C7—C8—C13—N9	−178.60 (10)
C2—C1—C10—N9	158.35 (9)	C7—C8—C13—C12	1.70 (15)
C2—C1—C10—C11	−21.72 (13)	C5—C12—C13—C8	−2.64 (14)
N9—C10—C11—C4	174.61 (9)	C11—C12—C13—C8	178.27 (9)
C1—C10—C11—C4	−5.33 (15)	C5—C12—C13—N9	177.61 (8)
N9—C10—C11—C12	−1.56 (11)	C11—C12—C13—N9	−1.47 (10)
C1—C10—C11—C12	178.50 (9)	C11—C10—N9—C13	0.66 (11)
C3—C4—C11—C10	2.22 (13)	C1—C10—N9—C13	−179.40 (9)
S1—C4—C11—C10	−174.91 (7)	C8—C13—N9—C10	−179.18 (10)
C3—C4—C11—C12	177.20 (10)	C12—C13—N9—C10	0.55 (11)
S1—C4—C11—C12	0.08 (16)

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁NS
M_r	201.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	90
a, b, c (Å)	8.6353 (14), 12.1395 (15), 9.5808 (14)
β (°)	104.599 (10)
V (Å³)	971.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.38 × 0.33 × 0.15

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.900, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	6145, 3305, 2915
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.741

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.087, 1.04
No. of reflections	3305
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.30

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Footnotes

‡Current address: Winston-Salem State University, Winston-Salem, NC 27110, USA.

§Current address: University of South Florida, Tampa, Florida 33620, USA.

Acknowledgements

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

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