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Acta Cryst. (2008). E64, o749    [ doi:10.1107/S1600536808007678 ]

3-Bromomethyl-2-chloromethyl-1-phenylsulfonyl-1H-indole

G. Chakkaravarthi, V. Dhayalan, A. K. Mohanakrishnan and V. Manivannan

Abstract top

In the title compound, C16H13BrClNO2S, the indole mean plane forms a dihedral angle of 73.59 (19)° with the phenyl ring. The molecular structure is stabilized by weak intramolecular C-H...O interactions. The Br atom is disordered over two positions with site occupancy factors of 0.7 and 0.3.

Comment top

In continuation of our studies of indole derivatives, which are known to exhibit anti-oxidant activity (Olgen & Coban, 2003), antihepatitis B virus activities (Chai et al., 2006) and antibacterial (Nieto et al., 2005) activities, we report the crystal structure of the title compound (I).

The geometric parameters of the molecule of (I) (Fig. 1) agree well with the reported structures (Chakkaravarthi et al., 2007, 2008). The indole mean plane forms a dihedral angle of 73.59 (19)° with the phenyl ring. The N1—S1—C1 plane is almost orthogonal to indole ring (dihedral angle 82.30 (22)°) and makes 76.93 (22)° with the phenyl ring. The indole mean plane and C8—C16—BR1 plane are nearly orthogonal to each other forming a dihedral angle of 82.23 (0.29)°.

The sum of bond angles around N1 (359.99°) shows that N1 is sp2-hybridized. The torsion angles O1—S1—N1—C14 and O2—S1—N1—C7 [17.8 (6)° and -33.4 (6)°, respectively] indicate the syn conformation of the sulfonyl moiety. The molecular structure is stabilized by weak intramolecular C—H···O interactions.

Related literature top

For related crystal structures, see: Chakkaravarthi et al. (2007, 2008). For the biological activities of indole derivatives, see: Chai et al. (2006); Nieto et al. (2005); Olgen & Coban (2003).

Experimental top

1-(Phenylsulfonyl)-3-(bromomethyl)-2-methylindole (0.5 g, 1.37 mmol) was dissolved in dry ccl4(10 ml) and then powdered N-chloro succinimide was added. To this, azobisisobutyronitrle (50 mg) was also added and then refluxed for 2 h on a waterbath. After the reaction was completed, succinimide was floated on the surface of the reaction mixture. It was then filtered off and washed with CCl4 (3 ml). The solvent was removed carefully under vacuo. The crude product was recrystallized from CCl4. Yield:76 percentage.

Refinement top

H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H and C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for CH2. The Br atom is disordered over two positions with the occupancies of 0.709 (16) and 0.291 (16), respectively. The distances C1—C2, C2—C3, C3—C4, C4—C5, C10—C11 and C11—C12 were restrained to 1.395 (1) Å, the distances C16—BR1 and C16—Br1A were restrained to 1.91 (10) Å and the distance CL1—C15 was restrained to 1.76 (5) Å. The anisotropic thermal parameters of C15, C16, BR1, BR1A, CL1 atoms were restrained with DELU in the final cycles of the refinement (Sheldrick, 2008).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atomic labels and 50% probability displacement ellipsoids for non-H atoms. Only major parts of the disordered atoms are drawn. Intramolecular H-bonds are shown as dashed lines.
3-Bromomethyl-2-chloromethyl-1-phenylsulfonyl-1H-indole top
Crystal data top
C16H13BrClNO2SF000 = 800
Mr = 398.69Dx = 1.682 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4037 reflections
a = 11.8501 (9) Åθ = 2.5–25.0º
b = 16.3525 (13) ŵ = 2.92 mm−1
c = 8.5793 (6) ÅT = 295 (2) K
β = 108.766 (3)ºBlock, colourless
V = 1574.1 (2) Å30.16 × 0.14 × 0.14 mm
Z = 4
Data collection top
Bruker Kappa APEXII
diffractometer		2770 independent reflections
Radiation source: fine-focus sealed tube1822 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
T = 295(2) Kθmax = 25.0º
ω and φ scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→13
Tmin = 0.559, Tmax = 0.665k = −19→19
14367 measured reflectionsl = −10→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.231  w = 1/[σ2(Fo2) + (0.127P)2 + 1.9456P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2770 reflectionsΔρmax = 0.42 e Å−3
209 parametersΔρmin = −0.91 e Å−3
12 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C16H13BrClNO2SV = 1574.1 (2) Å3
Mr = 398.69Z = 4
Monoclinic, P21/cMo Kα
a = 11.8501 (9) ŵ = 2.92 mm−1
b = 16.3525 (13) ÅT = 295 (2) K
c = 8.5793 (6) Å0.16 × 0.14 × 0.14 mm
β = 108.766 (3)º
Data collection top
Bruker Kappa APEXII
diffractometer		2770 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1822 reflections with I > 2σ(I)
Tmin = 0.559, Tmax = 0.665Rint = 0.045
14367 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06612 restraints
wR(F2) = 0.231H-atom parameters constrained
S = 1.06Δρmax = 0.42 e Å−3
2770 reflectionsΔρmin = −0.91 e Å−3
209 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.90925 (16)−0.10531 (12)0.5085 (3)0.0872 (6)
Br10.8135 (6)0.1043 (5)0.3205 (5)0.1572 (16)0.709 (16)
Br1A0.7901 (4)0.1251 (3)0.3139 (9)0.093 (2)0.291 (16)
S10.70049 (14)−0.13649 (11)0.8192 (2)0.0743 (6)
O10.6340 (5)−0.1191 (4)0.9258 (8)0.114 (2)
O20.6743 (5)−0.2077 (3)0.7212 (8)0.109 (2)
N10.6795 (4)−0.0573 (3)0.6922 (5)0.0539 (11)
C10.8512 (6)−0.1369 (4)0.9320 (7)0.0655 (17)
C20.8952 (7)−0.0826 (5)1.0604 (8)0.097 (2)
H20.8449−0.04491.08540.117*
C31.0161 (8)−0.0849 (8)1.1523 (11)0.127 (4)
H31.0474−0.04851.23870.153*
C41.0885 (9)−0.1418 (7)1.1133 (13)0.122 (4)
H41.1688−0.14411.17530.147*
C51.0442 (8)−0.1951 (6)0.9845 (13)0.113 (3)
H51.0947−0.23250.95900.135*
C60.9256 (7)−0.1932 (5)0.8934 (10)0.086 (2)
H60.8953−0.22950.80650.103*
C70.7000 (5)−0.0556 (3)0.5384 (7)0.0574 (14)
C80.6681 (5)0.0197 (3)0.4715 (6)0.0535 (14)
C90.6288 (5)0.0680 (3)0.5809 (5)0.0463 (12)
C100.5887 (6)0.1477 (4)0.5707 (7)0.0622 (15)
H100.58370.17960.47900.075*
C110.5563 (6)0.1790 (4)0.6984 (8)0.078 (2)
H110.52950.23270.69390.094*
C120.5633 (7)0.1313 (5)0.8332 (9)0.083 (2)
H120.54060.15370.91820.099*
C130.6026 (6)0.0519 (5)0.8471 (6)0.0687 (18)
H130.60640.02030.93880.082*
C140.6365 (4)0.0206 (3)0.7184 (6)0.0468 (12)
C150.7557 (4)−0.1232 (4)0.4743 (11)0.086 (2)
H15A0.7151−0.12940.35720.103*
H15B0.7464−0.17390.52780.103*
C160.6722 (5)0.0443 (4)0.3064 (7)0.084 (2)
H16A0.60300.07770.25200.101*0.709 (16)
H16B0.6686−0.00420.24000.101*0.709 (16)
H16C0.60520.08020.25600.101*0.291 (16)
H16D0.6645−0.00330.23630.101*0.291 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0663 (11)0.0872 (13)0.1176 (15)0.0181 (9)0.0429 (10)−0.0109 (10)
Br10.235 (3)0.159 (3)0.106 (2)−0.112 (2)0.095 (2)−0.0245 (15)
Br1A0.063 (4)0.105 (3)0.098 (3)−0.014 (2)0.008 (2)0.041 (3)
S10.0540 (9)0.0688 (11)0.0926 (12)−0.0071 (8)0.0129 (8)0.0402 (9)
O10.082 (3)0.142 (5)0.130 (5)0.015 (3)0.053 (3)0.087 (4)
O20.087 (3)0.059 (3)0.144 (5)−0.029 (3)−0.016 (3)0.035 (3)
N10.057 (3)0.049 (3)0.052 (2)0.000 (2)0.012 (2)0.013 (2)
C10.061 (4)0.067 (4)0.065 (4)−0.010 (3)0.015 (3)0.028 (3)
C20.100 (6)0.123 (7)0.058 (4)−0.002 (5)0.010 (4)0.011 (4)
C30.123 (8)0.145 (10)0.079 (6)−0.039 (8)−0.016 (6)0.010 (6)
C40.077 (6)0.138 (9)0.121 (8)−0.020 (6)−0.010 (6)0.051 (7)
C50.076 (6)0.116 (7)0.139 (8)0.024 (5)0.025 (6)0.041 (7)
C60.072 (5)0.077 (5)0.096 (5)0.011 (4)0.009 (4)0.019 (4)
C70.064 (4)0.051 (3)0.059 (3)−0.005 (3)0.023 (3)−0.008 (3)
C80.070 (4)0.053 (3)0.039 (3)−0.007 (3)0.020 (2)−0.002 (2)
C90.047 (3)0.052 (3)0.034 (2)−0.002 (2)0.005 (2)−0.001 (2)
C100.066 (4)0.050 (3)0.061 (3)0.006 (3)0.007 (3)0.005 (3)
C110.066 (4)0.066 (4)0.095 (5)0.014 (3)0.014 (4)−0.021 (4)
C120.071 (4)0.106 (6)0.073 (4)0.003 (4)0.028 (4)−0.036 (4)
C130.062 (4)0.104 (5)0.037 (3)−0.001 (4)0.013 (3)−0.002 (3)
C140.043 (3)0.057 (3)0.038 (2)−0.003 (2)0.009 (2)0.004 (2)
C150.079 (3)0.074 (5)0.110 (6)−0.007 (4)0.039 (4)−0.026 (4)
C160.134 (5)0.073 (4)0.051 (3)−0.026 (4)0.038 (4)0.001 (3)
Geometric parameters (Å, °) top
Cl1—C151.772 (4)C7—C81.359 (8)
Br1—C161.9114 (11)C7—C151.481 (9)
Br1A—C161.9084 (11)C8—C91.415 (8)
S1—O21.411 (6)C8—C161.489 (7)
S1—O11.415 (6)C9—C101.381 (8)
S1—N11.659 (4)C9—C141.390 (7)
S1—C11.737 (6)C10—C111.371 (7)
N1—C141.417 (7)C10—H100.9300
N1—C71.417 (7)C11—C121.375 (8)
C1—C21.380 (8)C11—H110.9300
C1—C61.386 (10)C12—C131.372 (10)
C2—C31.396 (8)C12—H120.9300
C2—H20.9300C13—C141.387 (8)
C3—C41.379 (9)C13—H130.9300
C3—H30.9300C15—H15A0.9700
C4—C51.371 (9)C15—H15B0.9700
C4—H40.9300C16—H16A0.9700
C5—C61.371 (12)C16—H16B0.9700
C5—H50.9300C16—H16C0.9700
C6—H60.9300C16—H16D0.9700
O2—S1—O1119.3 (4)C9—C10—H10120.6
O2—S1—N1107.2 (3)C10—C11—C12120.3 (6)
O1—S1—N1105.7 (3)C10—C11—H11119.9
O2—S1—C1108.5 (3)C12—C11—H11119.9
O1—S1—C1109.1 (4)C13—C12—C11122.5 (6)
N1—S1—C1106.2 (3)C13—C12—H12118.8
C14—N1—C7108.0 (4)C11—C12—H12118.8
C14—N1—S1125.7 (4)C12—C13—C14117.1 (6)
C7—N1—S1126.3 (4)C12—C13—H13121.4
C2—C1—C6120.8 (7)C14—C13—H13121.4
C2—C1—S1119.9 (6)C13—C14—C9120.9 (5)
C6—C1—S1119.3 (5)C13—C14—N1131.9 (5)
C1—C2—C3119.3 (8)C9—C14—N1107.2 (4)
C1—C2—H2120.4C7—C15—Cl1111.8 (4)
C3—C2—H2120.4C7—C15—H15A109.3
C4—C3—C2119.1 (9)Cl1—C15—H15A109.3
C4—C3—H3120.4C7—C15—H15B109.3
C2—C3—H3120.4Cl1—C15—H15B109.3
C5—C4—C3121.2 (9)H15A—C15—H15B107.9
C5—C4—H4119.4C8—C16—Br1A113.8 (4)
C3—C4—H4119.4C8—C16—Br1112.0 (4)
C6—C5—C4120.1 (9)C8—C16—H16A109.2
C6—C5—H5119.9Br1A—C16—H16A97.1
C4—C5—H5119.9Br1—C16—H16A109.2
C5—C6—C1119.5 (8)C8—C16—H16B109.2
C5—C6—H6120.3Br1A—C16—H16B118.6
C1—C6—H6120.3Br1—C16—H16B109.2
C8—C7—N1107.6 (5)H16A—C16—H16B107.9
C8—C7—C15128.1 (6)C8—C16—H16C108.4
N1—C7—C15124.2 (6)Br1A—C16—H16C94.7
C7—C8—C9109.4 (5)Br1—C16—H16C107.0
C7—C8—C16123.8 (6)H16B—C16—H16C111.0
C9—C8—C16126.7 (5)C8—C16—H16D110.3
C10—C9—C14120.5 (5)Br1A—C16—H16D119.9
C10—C9—C8131.7 (5)Br1—C16—H16D110.9
C14—C9—C8107.8 (5)H16A—C16—H16D104.9
C11—C10—C9118.7 (5)H16C—C16—H16D108.0
C11—C10—H10120.6
O2—S1—N1—C14146.0 (5)C15—C7—C8—C167.1 (9)
O1—S1—N1—C1417.8 (6)C7—C8—C9—C10179.3 (6)
C1—S1—N1—C14−98.1 (5)C16—C8—C9—C10−2.1 (10)
O2—S1—N1—C7−33.4 (6)C7—C8—C9—C14−0.3 (6)
O1—S1—N1—C7−161.6 (5)C16—C8—C9—C14178.3 (5)
C1—S1—N1—C782.5 (5)C14—C9—C10—C11−0.2 (8)
O2—S1—C1—C2−167.5 (6)C8—C9—C10—C11−179.8 (6)
O1—S1—C1—C2−36.0 (6)C9—C10—C11—C12−0.4 (10)
N1—S1—C1—C277.6 (6)C10—C11—C12—C130.3 (11)
O2—S1—C1—C611.3 (6)C11—C12—C13—C140.4 (10)
O1—S1—C1—C6142.8 (5)C12—C13—C14—C9−0.9 (8)
N1—S1—C1—C6−103.7 (5)C12—C13—C14—N1−179.4 (6)
C6—C1—C2—C3−0.2 (11)C10—C9—C14—C130.9 (8)
S1—C1—C2—C3178.6 (7)C8—C9—C14—C13−179.4 (5)
C1—C2—C3—C4−0.5 (15)C10—C9—C14—N1179.7 (5)
C2—C3—C4—C51.1 (17)C8—C9—C14—N1−0.6 (6)
C3—C4—C5—C6−1.0 (16)C7—N1—C14—C13179.9 (6)
C4—C5—C6—C10.3 (13)S1—N1—C14—C130.4 (8)
C2—C1—C6—C50.2 (11)C7—N1—C14—C91.3 (6)
S1—C1—C6—C5−178.5 (6)S1—N1—C14—C9−178.2 (4)
C14—N1—C7—C8−1.5 (6)C8—C7—C15—Cl176.0 (8)
S1—N1—C7—C8178.0 (4)N1—C7—C15—Cl1−98.7 (7)
C14—N1—C7—C15174.1 (5)C7—C8—C16—Br1A−112.1 (6)
S1—N1—C7—C15−6.4 (8)C9—C8—C16—Br1A69.5 (8)
N1—C7—C8—C91.1 (6)C7—C8—C16—Br1−98.2 (7)
C15—C7—C8—C9−174.3 (5)C9—C8—C16—Br183.4 (8)
N1—C7—C8—C16−177.5 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O20.932.512.877 (9)104
C13—H13···O10.932.312.873 (10)118
C15—H15B···O20.972.172.939 (10)136
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O20.932.512.877 (9)104
C13—H13···O10.932.312.873 (10)118
C15—H15B···O20.972.172.939 (10)136
Acknowledgements top

The authors acknowledge the Sophisticated Analytical Instrument Facility, Indian Institute of Technology, Madras, for the data collection.

references
References top

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Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.