5-Chloro-1-(4-methyl­phenyl­sulfon­yl)-1H-indole

Hassam, M.; Smith, V.J.

doi:10.1107/S1600536812046466

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3357

doi:10.1107/S1600536812046466

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5-Chloro-1-(4-methylphenylsulfonyl)-1H-indole

Mohammad Hassam ^a ^* and Vincent J. Smith ^a

^aDepartment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa
^*Correspondence e-mail: hassam@sun.ac.za

(Received 15 October 2012; accepted 9 November 2012; online 17 November 2012)

In the title compound, C₁₅H₁₂ClNO₂S, the indole ring is essentially planar (r.m.s. deviation = 0.0107 Å) and makes a dihedral angle of 85.01 (6)° with the benzene ring. In the crystal, three C—H⋯O hydrogen bonds result in a hydrogen-bonded spiral running parallel to the c axis.

Related literature

For background to the use of indoles as scaffolds in the synthesis of HIV-agents, see: Hassam et al. (2012 ). For the crystal structure of a closely related compound, see: Beddoes et al. (1986 ).

Experimental

Crystal data

C₁₅H₁₂ClNO₂S
M_r = 305.77
Tetragonal, I 4₁ /a
a = 26.991 (7) Å
c = 7.8345 (19) Å
V = 5708 (2) Å³
Z = 16
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 111 K
0.1 × 0.1 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.950, T_max = 0.968
17940 measured reflections
3565 independent reflections
2760 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.101
S = 1.06
3565 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.95	2.54	3.327 (2)	140
C4—H4⋯O1ⁱⁱ	0.95	2.49	3.192 (2)	131
C14—H14⋯O1ⁱⁱⁱ	0.95	2.59	3.333 (2)	135
Symmetry codes: (i) $[y-{\script{1\over 4}}, -x+{\script{3\over 4}}, z+{\script{3\over 4}}]$ ; (ii) x, y, z+1; (iii) $[-y+{\script{3\over 4}}, x+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ; Atwood & Barbour, 2003 ); software used to prepare material for publication: X-SEED.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046466/pv2597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046466/pv2597Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046466/pv2597Isup3.cml

checkCIF report

Comment top

5-Chloroindole is frequently employed as a building block in the synthesis of various biologically active molecules (Hassam et al., 2012). For this communication, tosylation of 5-chloroindole was performed by deprotonation of the indole with sodium hydride, followed by the addition of tosyl chloride.

In the title molecule (Fig. 1), the indole ring is essentially planar (rmsd = 0.0107 Å) with Cl1 lying in its plane (deviation 0.008 (2) Å). The dihedral angle between the mean planes of the indole and benzene rings is 85.01 (6)°. The bond distances and angles in the title compound agree very well with the corresponding bond distances and angles reported for 1-phenylsulfonyl-indole (Beddoes et al., 1986). There are three C—H···O hydrogen bonds which connect four symmetry related molecules into a hydrogen bonded spiral that runs parallel to the c-axis (Table 1 and Fig. 2).

Related literature top

For background to the use of indoles as scaffolds in the synthesis of HIV-agents, see: Hassam et al. (2012). For the crystal structure of a closely related compound, see: Beddoes et al. (1986).

Experimental top

Sodium hydride (0.325 g, 14.1 mmol) was added to a solution of 5-chloroindole (1.00 g, 6.59 mmol) in dry THF (50 ml) at 273.15 K (ice bath). The reaction mixture was stirred at the same temperature for 10 min, followed by addition of tosyl chloride (4-methyl-benzene-1-sulfonyl chloride, 1.88 g, 9.86 mmol). The reaction mixture was then stirred at 273.15 K for 2 h. Water (25 ml) was added to the flask and the mixture was extracted with diethyl ether (2 x 25 ml). The organic layer was washed with brine (25 ml) and dried over anhydrous sodium sulfate. Solvent was removed under vacuum and the resulting residue was recrystallized from hexane and dichloromethane (4:1) to obtain the title compound as a colourless crystalline material (1.61 g, 80%).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: X-SEED (Barbour, 2001; Atwood & Barbour, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the C—-H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen- bonding were omitted for clarity.

5-Chloro-1-(4-methylphenylsulfonyl)-1H-indole top

Crystal data top

C₁₅H₁₂ClNO₂S	D_x = 1.423 Mg m⁻³
M_r = 305.77	Melting point: 383 K
Tetragonal, I4₁/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 4ad	Cell parameters from 3900 reflections
a = 26.991 (7) Å	θ = 3.0–25.8°
c = 7.8345 (19) Å	µ = 0.41 mm⁻¹
V = 5708 (2) Å³	T = 111 K
Z = 16	Plate, colourless
F(000) = 2528	0.1 × 0.1 × 0.01 mm

Data collection top

Bruker APEXII CCD diffractometer	3565 independent reflections
Radiation source: fine-focus sealed tube, Bruker SMART APEXII	2760 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 28.9°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −36→26
T_min = 0.950, T_max = 0.968	k = −36→30
17940 measured reflections	l = −10→9

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0395P)² + 5.9559P] where P = (F_o² + 2F_c²)/3
3565 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₅H₁₂ClNO₂S	Z = 16
M_r = 305.77	Mo Kα radiation
Tetragonal, I4₁/a	µ = 0.41 mm⁻¹
a = 26.991 (7) Å	T = 111 K
c = 7.8345 (19) Å	0.1 × 0.1 × 0.01 mm
V = 5708 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	3565 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2760 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.968	R_int = 0.038
17940 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.06	Δρ_max = 0.31 e Å⁻³
3565 reflections	Δρ_min = −0.36 e Å⁻³
182 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	0.309589 (17)	0.612848 (17)	0.38622 (6)	0.02904 (13)
Cl1	0.494357 (19)	0.67701 (2)	0.99440 (8)	0.04639 (17)
C9	0.27756 (6)	0.66717 (7)	0.4379 (2)	0.0244 (4)
N1	0.33623 (5)	0.59487 (5)	0.56768 (19)	0.0257 (3)
O2	0.27557 (6)	0.57429 (5)	0.34641 (19)	0.0423 (4)
C1	0.31014 (7)	0.56870 (7)	0.6945 (3)	0.0306 (4)
H1	0.2805	0.5505	0.6762	0.037*
C5	0.44798 (7)	0.65358 (7)	0.8611 (3)	0.0304 (4)
O1	0.34919 (5)	0.62485 (6)	0.27270 (16)	0.0384 (3)
C4	0.41247 (7)	0.62301 (7)	0.9286 (2)	0.0299 (4)
H4	0.4129	0.6143	1.0461	0.036*
C8	0.37656 (6)	0.61872 (6)	0.6465 (2)	0.0223 (3)
C6	0.44862 (7)	0.66693 (7)	0.6895 (3)	0.0321 (4)
H6	0.4741	0.6879	0.6477	0.039*
C7	0.41247 (7)	0.64987 (7)	0.5795 (2)	0.0282 (4)
H7	0.4122	0.6591	0.4625	0.034*
C3	0.37571 (6)	0.60502 (6)	0.8196 (2)	0.0245 (4)
C11	0.27459 (7)	0.75507 (7)	0.4642 (3)	0.0324 (4)
H11	0.2898	0.7865	0.4496	0.039*
C10	0.30006 (7)	0.71282 (7)	0.4162 (2)	0.0290 (4)
H10	0.3324	0.7151	0.3692	0.035*
C2	0.33347 (7)	0.57340 (7)	0.8452 (2)	0.0306 (4)
H2	0.3238	0.5585	0.9499	0.037*
C12	0.22732 (7)	0.75243 (7)	0.5330 (2)	0.0298 (4)
C14	0.23055 (7)	0.66336 (7)	0.5066 (3)	0.0325 (4)
H14	0.2155	0.6319	0.5215	0.039*
C13	0.20586 (7)	0.70613 (8)	0.5533 (3)	0.0343 (4)
H13	0.1735	0.7038	0.6002	0.041*
C15	0.19970 (8)	0.79851 (8)	0.5824 (3)	0.0417 (5)
H15A	0.1849	0.7940	0.6956	0.063*
H16B	0.1735	0.8050	0.4987	0.063*
H17C	0.2227	0.8266	0.5851	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0320 (3)	0.0321 (3)	0.0230 (2)	0.00953 (18)	−0.00349 (18)	−0.00451 (18)
Cl1	0.0310 (3)	0.0522 (3)	0.0560 (3)	0.0064 (2)	−0.0073 (2)	−0.0294 (3)
C9	0.0226 (8)	0.0297 (9)	0.0209 (8)	0.0049 (7)	−0.0012 (7)	−0.0012 (7)
N1	0.0264 (8)	0.0276 (8)	0.0231 (7)	0.0022 (6)	−0.0005 (6)	0.0019 (6)
O2	0.0480 (9)	0.0340 (8)	0.0448 (9)	0.0065 (6)	−0.0175 (7)	−0.0127 (7)
C1	0.0291 (10)	0.0247 (9)	0.0382 (10)	−0.0007 (7)	0.0041 (8)	0.0034 (8)
C5	0.0243 (9)	0.0296 (9)	0.0375 (10)	0.0075 (7)	−0.0022 (8)	−0.0120 (8)
O1	0.0414 (8)	0.0520 (9)	0.0218 (6)	0.0217 (7)	0.0058 (6)	0.0028 (6)
C4	0.0309 (10)	0.0356 (10)	0.0230 (9)	0.0116 (8)	0.0002 (7)	−0.0038 (8)
C8	0.0226 (8)	0.0221 (8)	0.0224 (8)	0.0063 (6)	0.0019 (7)	0.0009 (6)
C6	0.0243 (9)	0.0261 (9)	0.0460 (11)	0.0023 (7)	0.0051 (8)	−0.0002 (8)
C7	0.0268 (9)	0.0296 (9)	0.0283 (9)	0.0054 (7)	0.0062 (7)	0.0056 (7)
C3	0.0262 (9)	0.0243 (8)	0.0230 (8)	0.0079 (7)	0.0039 (7)	0.0019 (7)
C11	0.0338 (10)	0.0267 (9)	0.0368 (11)	0.0006 (8)	0.0011 (8)	0.0051 (8)
C10	0.0234 (9)	0.0347 (10)	0.0287 (9)	0.0025 (7)	0.0048 (7)	0.0051 (8)
C2	0.0327 (10)	0.0302 (10)	0.0288 (10)	0.0028 (7)	0.0048 (8)	0.0083 (8)
C12	0.0312 (10)	0.0360 (10)	0.0221 (9)	0.0096 (8)	−0.0027 (7)	−0.0014 (8)
C14	0.0240 (9)	0.0331 (10)	0.0405 (11)	−0.0029 (7)	0.0030 (8)	−0.0014 (8)
C13	0.0219 (9)	0.0430 (11)	0.0379 (11)	0.0040 (8)	0.0075 (8)	−0.0015 (9)
C15	0.0483 (13)	0.0416 (12)	0.0352 (11)	0.0223 (10)	−0.0008 (9)	−0.0042 (9)

Geometric parameters (Å, º) top

S1—O2	1.4224 (15)	C6—C7	1.381 (3)
S1—O1	1.4278 (15)	C6—H6	0.9500
S1—N1	1.6654 (15)	C7—H7	0.9500
S1—C9	1.7496 (18)	C3—C2	1.438 (3)
Cl1—C5	1.7487 (19)	C11—C10	1.383 (3)
C9—C14	1.382 (2)	C11—C12	1.387 (3)
C9—C10	1.384 (3)	C11—H11	0.9500
N1—C8	1.407 (2)	C10—H10	0.9500
N1—C1	1.408 (2)	C2—H2	0.9500
C1—C2	1.345 (3)	C12—C13	1.387 (3)
C1—H1	0.9500	C12—C15	1.501 (3)
C5—C4	1.371 (3)	C14—C13	1.382 (3)
C5—C6	1.392 (3)	C14—H14	0.9500
C4—C3	1.396 (3)	C13—H13	0.9500
C4—H4	0.9500	C15—H15A	0.9800
C8—C7	1.386 (2)	C15—H16B	0.9800
C8—C3	1.406 (2)	C15—H17C	0.9800

O2—S1—O1	120.84 (9)	C8—C7—H7	121.3
O2—S1—N1	104.64 (8)	C4—C3—C8	119.13 (17)
O1—S1—N1	105.94 (8)	C4—C3—C2	133.19 (17)
O2—S1—C9	110.18 (9)	C8—C3—C2	107.68 (16)
O1—S1—C9	108.90 (9)	C10—C11—C12	121.37 (18)
N1—S1—C9	105.07 (8)	C10—C11—H11	119.3
C14—C9—C10	121.13 (17)	C12—C11—H11	119.3
C14—C9—S1	118.77 (14)	C11—C10—C9	118.83 (17)
C10—C9—S1	120.05 (13)	C11—C10—H10	120.6
C8—N1—C1	107.88 (14)	C9—C10—H10	120.6
C8—N1—S1	125.11 (12)	C1—C2—C3	107.74 (16)
C1—N1—S1	122.18 (13)	C1—C2—H2	126.1
C2—C1—N1	109.77 (17)	C3—C2—H2	126.1
C2—C1—H1	125.1	C13—C12—C11	118.36 (17)
N1—C1—H1	125.1	C13—C12—C15	120.65 (18)
C4—C5—C6	122.48 (18)	C11—C12—C15	120.98 (19)
C4—C5—Cl1	119.19 (15)	C9—C14—C13	118.91 (18)
C6—C5—Cl1	118.33 (15)	C9—C14—H14	120.5
C5—C4—C3	118.06 (17)	C13—C14—H14	120.5
C5—C4—H4	121.0	C14—C13—C12	121.40 (17)
C3—C4—H4	121.0	C14—C13—H13	119.3
C7—C8—C3	122.42 (17)	C12—C13—H13	119.3
C7—C8—N1	130.71 (16)	C12—C15—H15A	109.5
C3—C8—N1	106.86 (15)	C12—C15—H16B	109.5
C7—C6—C5	120.51 (18)	H15A—C15—H16B	109.5
C7—C6—H6	119.7	C12—C15—H17C	109.5
C5—C6—H6	119.7	H15A—C15—H17C	109.5
C6—C7—C8	117.39 (17)	H16B—C15—H17C	109.5
C6—C7—H7	121.3

O2—S1—C9—C14	27.82 (18)	C5—C6—C7—C8	−1.0 (3)
O1—S1—C9—C14	162.50 (15)	C3—C8—C7—C6	0.9 (3)
N1—S1—C9—C14	−84.38 (16)	N1—C8—C7—C6	−178.52 (16)
O2—S1—C9—C10	−154.75 (15)	C5—C4—C3—C8	0.1 (2)
O1—S1—C9—C10	−20.06 (17)	C5—C4—C3—C2	−179.33 (18)
N1—S1—C9—C10	93.06 (16)	C7—C8—C3—C4	−0.5 (3)
O2—S1—N1—C8	172.54 (14)	N1—C8—C3—C4	179.06 (15)
O1—S1—N1—C8	43.81 (16)	C7—C8—C3—C2	179.10 (16)
C9—S1—N1—C8	−71.38 (15)	N1—C8—C3—C2	−1.36 (18)
O2—S1—N1—C1	−35.12 (16)	C12—C11—C10—C9	0.0 (3)
O1—S1—N1—C1	−163.85 (14)	C14—C9—C10—C11	−0.2 (3)
C9—S1—N1—C1	80.95 (15)	S1—C9—C10—C11	−177.58 (14)
C8—N1—C1—C2	−2.7 (2)	N1—C1—C2—C3	1.8 (2)
S1—N1—C1—C2	−159.19 (13)	C4—C3—C2—C1	179.22 (19)
C6—C5—C4—C3	−0.2 (3)	C8—C3—C2—C1	−0.3 (2)
Cl1—C5—C4—C3	179.67 (13)	C10—C11—C12—C13	0.1 (3)
C1—N1—C8—C7	−178.07 (17)	C10—C11—C12—C15	−179.14 (18)
S1—N1—C8—C7	−22.5 (3)	C10—C9—C14—C13	0.3 (3)
C1—N1—C8—C3	2.45 (18)	S1—C9—C14—C13	177.70 (15)
S1—N1—C8—C3	158.06 (12)	C9—C14—C13—C12	−0.2 (3)
C4—C5—C6—C7	0.7 (3)	C11—C12—C13—C14	0.0 (3)
Cl1—C5—C6—C7	−179.22 (14)	C15—C12—C13—C14	179.24 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.54	3.327 (2)	140
C4—H4···O1ⁱⁱ	0.95	2.49	3.192 (2)	131
C14—H14···O1ⁱⁱⁱ	0.95	2.59	3.333 (2)	135
C7—H7···O1	0.95	2.44	3.025 (2)	120
C10—H10···O1	0.95	2.59	2.943 (2)	102

Symmetry codes: (i) y−1/4, −x+3/4, z+3/4; (ii) x, y, z+1; (iii) −y+3/4, x+1/4, z+1/4.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂ClNO₂S
M_r	305.77
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	111
a, c (Å)	26.991 (7), 7.8345 (19)
V (Å³)	5708 (2)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.1 × 0.1 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.950, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	17940, 3565, 2760
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.101, 1.06
No. of reflections	3565
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.36

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Atwood & Barbour, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.54	3.327 (2)	140.0
C4—H4···O1ⁱⁱ	0.95	2.49	3.192 (2)	131.0
C14—H14···O1ⁱⁱⁱ	0.95	2.59	3.333 (2)	135.1

Symmetry codes: (i) y−1/4, −x+3/4, z+3/4; (ii) x, y, z+1; (iii) −y+3/4, x+1/4, z+1/4.

Acknowledgements

MH thanks Professor Willem A. L. van Otterlo and Dr S. C. Pelly for their valuable input and research oversight. Stellenbosch University's Science Faculty is also acknowledged for providing laboratory space and financial research support (Subcommittee B). The South African National Research Foundation (NRF), Pretoria, is also acknowledged for providing some research funds.

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