6-Chloro-3,4-di­hydro-9H-carbazol-1(2H)-one

Sridharan, M.; Prasad, K.J.R.; Gunaseelan, A.T.; Thiruvalluvar, A.; Butcher, R.J.

doi:10.1107/S1600536808023441

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1635

doi:10.1107/S1600536808023441

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6-Chloro-3,4-dihydro-9H-carbazol-1(2H)-one

M. Sridharan,^a K. J. Rajendra Prasad,^a A. Thomas Gunaseelan,^b A. Thiruvalluvar ^b ^* and R. J. Butcher ^c

^aDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, Tamilnadu, India, ^bPG Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: athiru@vsnl.net

(Received 21 July 2008; accepted 24 July 2008; online 31 July 2008)

The carbazole unit of the title molecule, C₁₂H₁₀ClNO, is not planar. The dihedral angle between the benzene and pyrrole rings is 1.35 (10)°. The cyclohexene ring adopts an envelope conformation. In the crystal structure, intermolecular N—H⋯O hydrogen bonds form centrosymmetric dimers.

Related literature

For a related structure with a non-planar carbazole unit, see: Sridharan et al. (2008 ).

Experimental

Crystal data

C₁₂H₁₀ClNO
M_r = 219.66
Monoclinic, P 2₁ /c
a = 10.4211 (5) Å
b = 5.6851 (3) Å
c = 17.0824 (10) Å
β = 100.239 (6)°
V = 995.93 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 200 (2) K
0.58 × 0.18 × 0.11 mm

Data collection

Oxford Diffraction R Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.923, T_max = 1.000 (expected range = 0.888–0.962)
10695 measured reflections
3909 independent reflections
1793 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.139
S = 0.88
3909 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 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
N9—H9⋯O1ⁱ	0.82 (2)	2.11 (2)	2.872 (2)	154 (2)
Symmetry code: (i) -x, -y, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023441/sj2518sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023441/sj2518Isup2.hkl

checkCIF report

Comment top

Sridharan et al. (2008) have reported the crystal structure of 6-Methoxy-2,3,4,9-tetrahydro-1H-carbazol-1-one, in which the carbazole unit is not planar. The molecular structure of the title compound, with atomic numbering scheme, is shown in Fig. 1. The carbazole unit of the title molecule is not planar. The dihedral angle between the benzene ring and the pyrrole ring is 1.35 (10)°. The cyclohexene ring adopts an envelope conformation. Intermolecular N9—H9···O1 (-x, -y, -z) hydrogen bonds form centrosymmetric dimers in the crystal structure, Fig. 2.

Related literature top

For a related structure with a non-planar carbazole unit, see: Sridharan et al. (2008).

Experimental top

A solution of 2-(2-(4-chlorophenyl)hydrazono)cyclohexanone (0.236 g, 0.001 mol) in a mixture of acetic acid (20 ml) and hydrochloric acid (5 ml) was refluxed on an oil bath pre-heated to 398–403 K for 2 h. The contents were then cooled and poured onto cold water with stirring. The brown solid which separated was purified by passing through a column of silica gel and eluting with (95:5 v/v) petroleum ether-ethyl acetate mixture to yield the title compound (0.153 g, 70%). This was recrystallized from ethanol.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are represented by spheres of arbitrary radius.
	Fig. 2. The molecular packing of the title compound, viewed down the b axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

6-Chloro-3,4-dihydro-9H-carbazol-1(2H)-one top

Crystal data top

C₁₂H₁₀ClNO	F(000) = 456
M_r = 219.66	D_x = 1.465 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 475(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4211 (5) Å	Cell parameters from 1948 reflections
b = 5.6851 (3) Å	θ = 4.6–34.7°
c = 17.0824 (10) Å	µ = 0.35 mm⁻¹
β = 100.239 (6)°	T = 200 K
V = 995.93 (9) Å³	Needle, colourless
Z = 4	0.58 × 0.18 × 0.11 mm

Data collection top

Oxford Diffraction R Gemini diffractometer	3909 independent reflections
Radiation source: fine-focus sealed tube	1793 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 10.5081 pixels mm^-1	θ_max = 34.7°, θ_min = 4.6°
ϕ and ω scans	h = −16→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −9→9
T_min = 0.923, T_max = 1.000	l = −27→19
10695 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ²(F_o²) + (0.0611P)²] where P = (F_o² + 2F_c²)/3
3909 reflections	(Δ/σ)_max = 0.001
140 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₀ClNO	V = 995.93 (9) Å³
M_r = 219.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4211 (5) Å	µ = 0.35 mm⁻¹
b = 5.6851 (3) Å	T = 200 K
c = 17.0824 (10) Å	0.58 × 0.18 × 0.11 mm
β = 100.239 (6)°

Data collection top

Oxford Diffraction R Gemini diffractometer	3909 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	1793 reflections with I > 2σ(I)
T_min = 0.923, T_max = 1.000	R_int = 0.072
10695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	Δρ_max = 0.46 e Å⁻³
3909 reflections	Δρ_min = −0.23 e Å⁻³
140 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Cl1	0.51516 (5)	0.81197 (10)	−0.14449 (3)	0.0418 (2)
O1	−0.02083 (14)	0.1402 (3)	0.10672 (9)	0.0403 (5)
N9	0.14769 (15)	0.2338 (3)	−0.00949 (10)	0.0293 (5)
C1	0.05496 (17)	0.3080 (3)	0.11410 (11)	0.0276 (5)
C2	0.06417 (19)	0.4778 (4)	0.18253 (12)	0.0340 (6)
C3	0.1973 (2)	0.5983 (4)	0.20336 (12)	0.0361 (6)
C4	0.2388 (2)	0.7173 (4)	0.13273 (12)	0.0358 (7)
C4A	0.22083 (17)	0.5536 (3)	0.06315 (11)	0.0258 (5)
C4B	0.28050 (17)	0.5475 (3)	−0.00559 (11)	0.0251 (5)
C5	0.36953 (17)	0.6955 (3)	−0.03472 (12)	0.0286 (5)
C6	0.40706 (18)	0.6321 (3)	−0.10471 (12)	0.0292 (6)
C7	0.36271 (19)	0.4274 (4)	−0.14660 (12)	0.0337 (6)
C8	0.27603 (19)	0.2811 (4)	−0.11885 (12)	0.0318 (6)
C8A	0.23419 (17)	0.3435 (3)	−0.04868 (11)	0.0260 (5)
C9A	0.13871 (17)	0.3614 (3)	0.05784 (11)	0.0253 (5)
H2A	−0.00399	0.59971	0.16903	0.0408*
H2B	0.04640	0.39204	0.22991	0.0408*
H3A	0.26364	0.47952	0.22511	0.0433*
H3B	0.19391	0.71695	0.24535	0.0433*
H4A	0.33155	0.76429	0.14653	0.0430*
H4B	0.18603	0.86099	0.11876	0.0430*
H5	0.40231	0.83389	−0.00698	0.0343*
H7	0.39275	0.38971	−0.19443	0.0404*
H8	0.24555	0.14153	−0.14666	0.0381*
H9	0.1137 (19)	0.107 (4)	−0.0230 (12)	0.023 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0407 (3)	0.0437 (3)	0.0464 (3)	−0.0017 (2)	0.0224 (2)	0.0095 (3)
O1	0.0350 (7)	0.0496 (9)	0.0389 (8)	−0.0151 (7)	0.0138 (7)	−0.0069 (8)
N9	0.0308 (8)	0.0319 (9)	0.0269 (8)	−0.0096 (7)	0.0095 (7)	−0.0062 (8)
C1	0.0222 (8)	0.0333 (10)	0.0273 (9)	0.0006 (8)	0.0046 (7)	0.0012 (9)
C2	0.0336 (10)	0.0437 (12)	0.0271 (10)	−0.0017 (9)	0.0119 (9)	−0.0023 (10)
C3	0.0424 (11)	0.0397 (12)	0.0279 (10)	−0.0077 (9)	0.0109 (9)	−0.0051 (10)
C4	0.0459 (12)	0.0306 (11)	0.0333 (11)	−0.0057 (9)	0.0138 (10)	−0.0061 (10)
C4A	0.0265 (9)	0.0262 (9)	0.0250 (9)	0.0022 (7)	0.0051 (8)	0.0012 (9)
C4B	0.0255 (8)	0.0275 (10)	0.0223 (9)	0.0020 (7)	0.0043 (7)	0.0035 (8)
C5	0.0302 (9)	0.0269 (10)	0.0294 (9)	−0.0009 (8)	0.0071 (8)	0.0023 (9)
C6	0.0273 (9)	0.0319 (11)	0.0305 (10)	0.0040 (7)	0.0113 (8)	0.0085 (9)
C7	0.0355 (10)	0.0412 (12)	0.0266 (9)	0.0051 (9)	0.0117 (9)	0.0005 (10)
C8	0.0344 (10)	0.0348 (11)	0.0276 (10)	−0.0007 (8)	0.0097 (8)	−0.0046 (9)
C8A	0.0244 (8)	0.0302 (10)	0.0240 (9)	0.0004 (7)	0.0057 (7)	0.0006 (9)
C9A	0.0240 (8)	0.0287 (10)	0.0238 (9)	0.0026 (7)	0.0056 (7)	0.0007 (8)

Geometric parameters (Å, º) top

Cl1—C6	1.7460 (19)	C5—C6	1.371 (3)
O1—C1	1.231 (2)	C6—C7	1.401 (3)
N9—C8A	1.365 (2)	C7—C8	1.373 (3)
N9—C9A	1.377 (2)	C8—C8A	1.392 (3)
N9—H9	0.82 (2)	C2—H2A	0.9900
C1—C9A	1.441 (3)	C2—H2B	0.9900
C1—C2	1.506 (3)	C3—H3A	0.9900
C2—C3	1.531 (3)	C3—H3B	0.9900
C3—C4	1.512 (3)	C4—H4A	0.9900
C4—C4A	1.495 (3)	C4—H4B	0.9900
C4A—C4B	1.424 (3)	C5—H5	0.9500
C4A—C9A	1.381 (2)	C7—H7	0.9500
C4B—C8A	1.412 (2)	C8—H8	0.9500
C4B—C5	1.407 (3)

Cl1···C4Aⁱ	3.5299 (19)	C8A···H2A^vi	2.8900
Cl1···H7ⁱⁱ	3.1000	C9A···H3A	3.0000
Cl1···H4Aⁱⁱⁱ	2.8900	C9A···H4B^v	3.0400
O1···N9	2.924 (2)	H2A···H2B^x	2.4900
O1···N9^iv	2.872 (2)	H2A···C8^vi	2.8900
O1···H4B^v	2.6600	H2A···C8A^vi	2.8900
O1···H9	2.83 (2)	H2B···H2A^xi	2.4900
O1···H9^iv	2.11 (2)	H3A···C9A	3.0000
N9···O1	2.924 (2)	H3A···C8^vii	3.0300
N9···O1^iv	2.872 (2)	H3A···H8^vii	2.3400
C4A···Cl1ⁱ	3.5299 (19)	H3B···C7^xii	3.0700
C5···C5ⁱ	3.549 (3)	H4A···Cl1ⁱⁱⁱ	2.8900
C5···C6ⁱ	3.548 (3)	H4B···O1^xiii	2.6600
C6···C5ⁱ	3.548 (3)	H4B···C1^xiii	2.8800
C9A···C9A^vi	3.566 (3)	H4B···C9A^xiii	3.0400
C1···H4B^v	2.8800	H7···Cl1^xiv	3.1000
C3···H8^vii	2.8700	H8···C3^ix	2.8700
C7···H3B^viii	3.0700	H8···H3A^ix	2.3400
C8···H2A^vi	2.8900	H9···O1	2.83 (2)
C8···H3A^ix	3.0300	H9···O1^iv	2.11 (2)

C8A—N9—C9A	108.53 (15)	C1—C9A—C4A	124.38 (17)
C9A—N9—H9	127.6 (14)	N9—C9A—C1	125.83 (16)
C8A—N9—H9	123.7 (14)	N9—C9A—C4A	109.78 (16)
O1—C1—C9A	123.29 (17)	C1—C2—H2A	109.00
O1—C1—C2	121.85 (17)	C1—C2—H2B	109.00
C2—C1—C9A	114.85 (16)	C3—C2—H2A	109.00
C1—C2—C3	113.41 (16)	C3—C2—H2B	109.00
C2—C3—C4	112.99 (17)	H2A—C2—H2B	108.00
C3—C4—C4A	110.04 (18)	C2—C3—H3A	109.00
C4B—C4A—C9A	106.44 (16)	C2—C3—H3B	109.00
C4—C4A—C4B	131.28 (17)	C4—C3—H3A	109.00
C4—C4A—C9A	122.24 (17)	C4—C3—H3B	109.00
C5—C4B—C8A	119.51 (17)	H3A—C3—H3B	108.00
C4A—C4B—C8A	106.93 (15)	C3—C4—H4A	110.00
C4A—C4B—C5	133.57 (17)	C3—C4—H4B	110.00
C4B—C5—C6	117.36 (16)	C4A—C4—H4A	110.00
Cl1—C6—C5	119.30 (14)	C4A—C4—H4B	110.00
Cl1—C6—C7	117.70 (15)	H4A—C4—H4B	108.00
C5—C6—C7	123.00 (17)	C4B—C5—H5	121.00
C6—C7—C8	120.30 (19)	C6—C5—H5	121.00
C7—C8—C8A	117.96 (19)	C6—C7—H7	120.00
N9—C8A—C8	129.85 (17)	C8—C7—H7	120.00
C4B—C8A—C8	121.86 (17)	C7—C8—H8	121.00
N9—C8A—C4B	108.29 (16)	C8A—C8—H8	121.00

C9A—N9—C8A—C4B	−0.6 (2)	C4—C4A—C4B—C8A	175.46 (19)
C9A—N9—C8A—C8	179.52 (19)	C9A—C4A—C4B—C5	178.3 (2)
C8A—N9—C9A—C1	178.12 (17)	C4B—C4A—C9A—N9	1.7 (2)
C8A—N9—C9A—C4A	−0.7 (2)	C4B—C4A—C9A—C1	−177.15 (17)
C2—C1—C9A—N9	−179.78 (17)	C4A—C4B—C8A—N9	1.6 (2)
C2—C1—C9A—C4A	−1.1 (3)	C5—C4B—C8A—C8	1.3 (3)
O1—C1—C2—C3	153.79 (19)	C4A—C4B—C8A—C8	−178.47 (18)
C9A—C1—C2—C3	−27.7 (2)	C5—C4B—C8A—N9	−178.63 (16)
O1—C1—C9A—N9	−1.3 (3)	C4A—C4B—C5—C6	179.7 (2)
O1—C1—C9A—C4A	177.38 (18)	C8A—C4B—C5—C6	0.0 (3)
C1—C2—C3—C4	53.7 (2)	C4B—C5—C6—Cl1	178.90 (14)
C2—C3—C4—C4A	−48.1 (2)	C4B—C5—C6—C7	−1.2 (3)
C3—C4—C4A—C4B	−157.05 (19)	Cl1—C6—C7—C8	−178.99 (16)
C3—C4—C4A—C9A	20.1 (3)	C5—C6—C7—C8	1.1 (3)
C4—C4A—C9A—N9	−176.05 (17)	C6—C7—C8—C8A	0.2 (3)
C4—C4A—C9A—C1	5.1 (3)	C7—C8—C8A—N9	178.52 (19)
C9A—C4A—C4B—C8A	−2.0 (2)	C7—C8—C8A—C4B	−1.4 (3)
C4—C4A—C4B—C5	−4.2 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y+1/2, −z−1/2; (iii) −x+1, −y+2, −z; (iv) −x, −y, −z; (v) x, y−1, z; (vi) −x, −y+1, −z; (vii) x, −y+1/2, z+1/2; (viii) x, −y+3/2, z−1/2; (ix) x, −y+1/2, z−1/2; (x) −x, y+1/2, −z+1/2; (xi) −x, y−1/2, −z+1/2; (xii) x, −y+3/2, z+1/2; (xiii) x, y+1, z; (xiv) −x+1, y−1/2, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O1^iv	0.82 (2)	2.11 (2)	2.872 (2)	154 (2)

Symmetry code: (iv) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀ClNO
M_r	219.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	10.4211 (5), 5.6851 (3), 17.0824 (10)
β (°)	100.239 (6)
V (Å³)	995.93 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.58 × 0.18 × 0.11

Data collection
Diffractometer	Oxford Diffraction R Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.923, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10695, 3909, 1793
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.801

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.139, 0.88
No. of reflections	3909
No. of parameters	140
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.23

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O1ⁱ	0.82 (2)	2.11 (2)	2.872 (2)	154 (2)

Symmetry code: (i) −x, −y, −z.

Acknowledgements

MS thanks the UGC, New Delhi, for the award of a research fellowship. KJR acknowledges the UGC, New Delhi, India, for the award of Major Research Project grant No. F.No.31–122/2005. AT thanks the UGC, India, for the award of a Minor Research Project [File No. MRP-2355/06(UGC-SERO), Link No. 2355, 10/01/2007]. RJB acknowledges the NSF–MRI program for funding to purchase the X-ray CCD diffractometer.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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