3,4-Dibromo-2,5-dimethyl-1-phenyl­sulfonyl-1H-pyrrole

Kanchanadevi, J.; Anbalagan, G.; Sureshbabu, R.; Mohanakrishnan, A.K.; Manivannan, V.

doi:10.1107/S1600536811030443

organic compounds

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Volume 67| Part 9| September 2011| Page o2224

doi:10.1107/S1600536811030443

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3,4-Dibromo-2,5-dimethyl-1-phenylsulfonyl-1H-pyrrole

J. Kanchanadevi,^a G. Anbalagan,^b R. Sureshbabu,^c A. K. Mohanakrishnan ^c and V. Manivannan ^d ^*

^aDepartment of Physics, Velammal Institute of Technology, Panchetty, Chennai 601 204, India, ^bDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^cDepartment of Organic Chemistry, University of Madras, Guindy campus, Chennai 600 025, India, and ^dDepartment of Research and Development, PRIST University, Vallam, Thanjavur 613 403, Tamil Nadu, India
^*Correspondence e-mail: crystallography2010@gmail.com, phdguna@gmail.com

(Received 14 July 2011; accepted 28 July 2011; online 2 August 2011)

In the title compound, C₁₂H₁₁Br₂NO₂S, the dihedral angle between the two rings is 78.79 (12)°. The crystal packing features C—H⋯π interactions.

Related literature

For the biological activity of heterocyclic compounds, see: Ali et al. (1989 ); Amal Raj et al. (2003 ). For related structures, see: Seshadri et al. (2009 ); Gunasekaran et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₁Br₂NO₂S
M_r = 393.10
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.6248 (4) Å
b = 9.7172 (6) Å
c = 21.2083 (11) Å
V = 1365.27 (14) Å³
Z = 4
Mo Kα radiation
μ = 6.08 mm⁻¹
T = 295 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.945, T_max = 0.955
9255 measured reflections
3491 independent reflections
2735 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.075
S = 1.02
3491 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.92 e Å⁻³
Absolute structure: Flack (1983 ), 1460 Friedel pairs
Flack parameter: 0.010 (10)

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯Cg2ⁱ	0.96	2.85	3.545 (7)	130
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S1600536811030443/bt5579sup1.cif

Supporting information file. DOI: 10.1107/S1600536811030443/bt5579globalsup2.cml

checkCIF report

Comment top

Heterocycles, especially five-membered rings, are involved in a wide range of biologically important chemical reactions in living organisms, and therefore they form one of the most important and well investigated classes of organic compounds. They have exhibit antifungal(Amal Raj et al., 2003) and fungicidal (Ali et al., 1989) activity.

The geometric parameters of the title molecule (Fig. 1) agree well with reported similar structure(Seshadri et al., 2009). The phenyl and pyrrole rings inclined at an angle of 78.79 (12) °. The sum of bond angles around N1 [359.6 (3) °] indicates the sp² hybridization state of atom N1 in the molecule.

The angular disposition of the bonds about the 'S' atom show significant deviation from that a regular tetrahedron, with the largest deviation in O—S—O angle. The widening of angle O1—S1—O2 = 120. 09 (18) ° from the ideal tetrahedral value is the result of the repulsive interactions between the short S=O bonds similar to that observed in other structures (Gunasekaran et al., 2009).

The molecular structure is stabilized by weak intramolecular C—H···O and C—H···Br interactions. The crystal packing is controlled by C—H···π [C12—H12A···Cg2(1 - x,-1/2 + y,1/2 - z) distance of 3.545 (7)Å (Cg2 is the centroid of the ring defined by the atoms C5—C10)] interaction.

Related literature top

For the biological activity of heterocyclic compounds, see: Ali et al. (1989); Amal Raj et al. (2003). For related structures, see: Seshadri et al. (2009); Gunasekaran et al. (2009).

Experimental top

To a solution of tertiary butoxide (1.33 g, 11.85 mmol) and 18-crown -6 (0.15 g, 0.59 mmol) in dry tetrahydrofuran (30 ml), 3,4-dibromo-2,5- dimethyl-1H-pyrrole (1.5 g, 5.92 mmol) was added. It was then stirred at room temperature for 30 minutes under nitrogen atmosphere. Then, phenylsulfonyl chloride (0.9 ml, 7.11 mmol) was added through syringe and stirred at the same temperature for 4 h. The reaction mixture was poured to water (100 ml) and extracted with ethylacetate (2 x 30 ml). The solvent was removed under reduced pressure.The solid obtained was recrystallized from chloroform to give pure product as a pale brown solid. The yield of the product is 65% and melting point is 515 K.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

3,4-Dibromo-2,5-dimethyl-1-phenylsulfonyl-1H-pyrrole top

Crystal data top

C₁₂H₁₁Br₂NO₂S	F(000) = 768
M_r = 393.10	D_x = 1.912 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7415 reflections
a = 6.6248 (4) Å	θ = 2.0–28.7°
b = 9.7172 (6) Å	µ = 6.08 mm⁻¹
c = 21.2083 (11) Å	T = 295 K
V = 1365.27 (14) Å³	Block, pale brown
Z = 4	0.35 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3491 independent reflections
Radiation source: fine-focus sealed tube	2735 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 0 pixels mm^-1	θ_max = 28.6°, θ_min = 1.9°
ω and ϕ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→10
T_min = 0.945, T_max = 0.955	l = −17→28
9255 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.029P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3491 reflections	Δρ_max = 0.47 e Å⁻³
165 parameters	Δρ_min = −0.92 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1460 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.010 (10)

Crystal data top

C₁₂H₁₁Br₂NO₂S	V = 1365.27 (14) Å³
M_r = 393.10	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.6248 (4) Å	µ = 6.08 mm⁻¹
b = 9.7172 (6) Å	T = 295 K
c = 21.2083 (11) Å	0.35 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3491 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2735 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.955	R_int = 0.027
9255 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.075	Δρ_max = 0.47 e Å⁻³
S = 1.02	Δρ_min = −0.92 e Å⁻³
3491 reflections	Absolute structure: Flack (1983), 1460 Friedel pairs
165 parameters	Absolute structure parameter: 0.010 (10)
0 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.1597 (5)	0.2073 (3)	0.41513 (14)	0.0293 (7)
C2	0.1708 (5)	0.0859 (3)	0.44645 (14)	0.0327 (8)
C3	0.3469 (6)	0.0151 (3)	0.42718 (15)	0.0329 (7)
C4	0.4461 (5)	0.0895 (3)	0.38337 (14)	0.0298 (7)
C5	0.2313 (6)	0.2831 (3)	0.25488 (15)	0.0327 (8)
C6	0.3161 (7)	0.1922 (4)	0.21200 (17)	0.0469 (10)
H6	0.4434	0.1548	0.2190	0.056*
C7	0.2079 (8)	0.1584 (4)	0.15883 (18)	0.0549 (11)
H7	0.2633	0.0990	0.1291	0.066*
C8	0.0186 (8)	0.2121 (4)	0.14939 (18)	0.0596 (13)
H8	−0.0538	0.1877	0.1135	0.072*
C9	−0.0642 (7)	0.3002 (5)	0.19171 (19)	0.0610 (12)
H9	−0.1935	0.3344	0.1850	0.073*
C10	0.0435 (6)	0.3399 (5)	0.24533 (17)	0.0499 (10)
H10	−0.0102	0.4030	0.2738	0.060*
C11	0.0040 (6)	0.3164 (4)	0.42098 (18)	0.0449 (9)
H11A	−0.0988	0.2870	0.4499	0.067*
H11B	−0.0552	0.3336	0.3804	0.067*
H11C	0.0655	0.3993	0.4364	0.067*
C12	0.6350 (6)	0.0542 (4)	0.34928 (18)	0.0474 (10)
H12A	0.6855	−0.0324	0.3643	0.071*
H12B	0.7340	0.1246	0.3565	0.071*
H12C	0.6077	0.0476	0.3049	0.071*
N1	0.3311 (4)	0.2116 (3)	0.37564 (12)	0.0285 (6)
O1	0.2928 (4)	0.4577 (2)	0.34533 (11)	0.0435 (6)
O2	0.5824 (4)	0.3247 (3)	0.30554 (12)	0.0448 (6)
S1	0.37395 (13)	0.33329 (9)	0.32099 (4)	0.03095 (19)
Br1	−0.00952 (7)	0.02664 (5)	0.50804 (2)	0.05823 (14)
Br2	0.43075 (7)	−0.15500 (4)	0.45930 (2)	0.05195 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0269 (18)	0.0320 (17)	0.0290 (17)	0.0039 (15)	0.0017 (15)	−0.0010 (14)
C2	0.0326 (19)	0.0388 (19)	0.0267 (18)	−0.0042 (16)	0.0028 (15)	−0.0001 (14)
C3	0.0411 (19)	0.0277 (16)	0.0299 (17)	0.0031 (15)	−0.0065 (15)	0.0011 (13)
C4	0.032 (2)	0.0269 (15)	0.0301 (17)	0.0053 (15)	−0.0025 (15)	−0.0039 (13)
C5	0.036 (2)	0.0324 (17)	0.0294 (18)	−0.0045 (16)	−0.0004 (15)	0.0039 (14)
C6	0.063 (3)	0.037 (2)	0.041 (2)	0.006 (2)	0.003 (2)	0.0050 (17)
C7	0.081 (3)	0.042 (2)	0.041 (2)	−0.006 (3)	−0.003 (2)	−0.0039 (19)
C8	0.075 (4)	0.068 (3)	0.036 (2)	−0.025 (3)	−0.008 (2)	0.005 (2)
C9	0.040 (2)	0.100 (4)	0.043 (2)	−0.002 (2)	−0.006 (2)	0.008 (2)
C10	0.039 (2)	0.075 (3)	0.036 (2)	0.004 (2)	0.0026 (17)	−0.0014 (18)
C11	0.046 (2)	0.045 (2)	0.044 (2)	0.014 (2)	0.011 (2)	−0.0015 (16)
C12	0.043 (2)	0.040 (2)	0.059 (2)	0.0122 (19)	0.012 (2)	0.0013 (18)
N1	0.0301 (16)	0.0276 (13)	0.0279 (13)	0.0044 (12)	0.0036 (13)	−0.0001 (12)
O1	0.0573 (17)	0.0265 (12)	0.0466 (15)	0.0032 (13)	0.0010 (13)	−0.0011 (11)
O2	0.0325 (13)	0.0490 (15)	0.0528 (15)	−0.0089 (13)	0.0050 (12)	0.0076 (12)
S1	0.0317 (4)	0.0273 (4)	0.0339 (4)	−0.0018 (4)	0.0008 (4)	0.0021 (3)
Br1	0.0557 (3)	0.0637 (3)	0.0552 (2)	0.0000 (2)	0.0204 (2)	0.0186 (2)
Br2	0.0661 (3)	0.03477 (19)	0.0549 (2)	0.0103 (2)	−0.0033 (2)	0.01168 (17)

Geometric parameters (Å, º) top

C1—C2	1.356 (4)	C7—H7	0.9300
C1—N1	1.412 (4)	C8—C9	1.356 (6)
C1—C11	1.484 (5)	C8—H8	0.9300
C2—C3	1.415 (5)	C9—C10	1.397 (5)
C2—Br1	1.861 (3)	C9—H9	0.9300
C3—C4	1.348 (5)	C10—H10	0.9300
C3—Br2	1.872 (3)	C11—H11A	0.9600
C4—N1	1.420 (4)	C11—H11B	0.9600
C4—C12	1.486 (5)	C11—H11C	0.9600
C5—C10	1.377 (5)	C12—H12A	0.9600
C5—C6	1.386 (5)	C12—H12B	0.9600
C5—S1	1.760 (3)	C12—H12C	0.9600
C6—C7	1.376 (5)	N1—S1	1.680 (3)
C6—H6	0.9300	O1—S1	1.420 (2)
C7—C8	1.373 (7)	O2—S1	1.422 (3)

C2—C1—N1	105.8 (3)	C10—C9—H9	119.8
C2—C1—C11	128.2 (3)	C5—C10—C9	118.1 (4)
N1—C1—C11	126.0 (3)	C5—C10—H10	121.0
C1—C2—C3	109.1 (3)	C9—C10—H10	121.0
C1—C2—Br1	125.3 (3)	C1—C11—H11A	109.5
C3—C2—Br1	125.5 (3)	C1—C11—H11B	109.5
C4—C3—C2	109.9 (3)	H11A—C11—H11B	109.5
C4—C3—Br2	125.4 (3)	C1—C11—H11C	109.5
C2—C3—Br2	124.7 (3)	H11A—C11—H11C	109.5
C3—C4—N1	105.4 (3)	H11B—C11—H11C	109.5
C3—C4—C12	128.5 (3)	C4—C12—H12A	109.5
N1—C4—C12	126.1 (3)	C4—C12—H12B	109.5
C10—C5—C6	121.7 (4)	H12A—C12—H12B	109.5
C10—C5—S1	119.4 (3)	C4—C12—H12C	109.5
C6—C5—S1	118.8 (3)	H12A—C12—H12C	109.5
C7—C6—C5	118.6 (4)	H12B—C12—H12C	109.5
C7—C6—H6	120.7	C1—N1—C4	109.8 (3)
C5—C6—H6	120.7	C1—N1—S1	124.5 (2)
C8—C7—C6	120.3 (4)	C4—N1—S1	125.3 (2)
C8—C7—H7	119.8	O1—S1—O2	120.09 (18)
C6—C7—H7	119.8	O1—S1—N1	106.52 (14)
C9—C8—C7	120.9 (4)	O2—S1—N1	106.36 (15)
C9—C8—H8	119.6	O1—S1—C5	108.82 (17)
C7—C8—H8	119.6	O2—S1—C5	108.76 (17)
C8—C9—C10	120.4 (4)	N1—S1—C5	105.30 (15)
C8—C9—H9	119.8

N1—C1—C2—C3	0.2 (4)	C2—C1—N1—C4	0.4 (3)
C11—C1—C2—C3	−178.7 (3)	C11—C1—N1—C4	179.3 (3)
N1—C1—C2—Br1	177.2 (2)	C2—C1—N1—S1	172.8 (2)
C11—C1—C2—Br1	−1.7 (5)	C11—C1—N1—S1	−8.3 (5)
C1—C2—C3—C4	−0.8 (4)	C3—C4—N1—C1	−0.9 (3)
Br1—C2—C3—C4	−177.8 (2)	C12—C4—N1—C1	178.9 (3)
C1—C2—C3—Br2	178.1 (2)	C3—C4—N1—S1	−173.2 (2)
Br1—C2—C3—Br2	1.1 (4)	C12—C4—N1—S1	6.5 (5)
C2—C3—C4—N1	1.0 (4)	C1—N1—S1—O1	33.9 (3)
Br2—C3—C4—N1	−177.9 (2)	C4—N1—S1—O1	−154.8 (3)
C2—C3—C4—C12	−178.7 (3)	C1—N1—S1—O2	163.1 (3)
Br2—C3—C4—C12	2.4 (5)	C4—N1—S1—O2	−25.6 (3)
C10—C5—C6—C7	−0.2 (6)	C1—N1—S1—C5	−81.6 (3)
S1—C5—C6—C7	−176.9 (3)	C4—N1—S1—C5	89.7 (3)
C5—C6—C7—C8	−1.2 (6)	C10—C5—S1—O1	−16.9 (3)
C6—C7—C8—C9	0.8 (6)	C6—C5—S1—O1	159.8 (3)
C7—C8—C9—C10	1.1 (7)	C10—C5—S1—O2	−149.4 (3)
C6—C5—C10—C9	2.0 (6)	C6—C5—S1—O2	27.4 (3)
S1—C5—C10—C9	178.6 (3)	C10—C5—S1—N1	96.9 (3)
C8—C9—C10—C5	−2.4 (7)	C6—C5—S1—N1	−86.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.93	2.57	2.922 (5)	103
C11—H11A···Br1	0.96	2.88	3.368 (4)	113
C11—H11C···O1	0.96	2.51	2.849 (5)	100
C12—H12A···Br2	0.96	2.88	3.378 (4)	113
C12—H12B···O2	0.96	2.44	2.809 (5)	102
C12—H12A···Cg2ⁱ	0.96	2.85	3.545 (7)	130

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁Br₂NO₂S
M_r	393.10
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	6.6248 (4), 9.7172 (6), 21.2083 (11)
V (Å³)	1365.27 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.08
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.945, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	9255, 3491, 2735
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.075, 1.02
No. of reflections	3491
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.92
Absolute structure	Flack (1983), 1460 Friedel pairs
Absolute structure parameter	0.010 (10)

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXL97.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.93	2.57	2.922 (5)	102.7
C11—H11A···Br1	0.96	2.88	3.368 (4)	113.0
C11—H11C···O1	0.96	2.51	2.849 (5)	100.4
C12—H12A···Br2	0.96	2.88	3.378 (4)	113.0
C12—H12B···O2	0.96	2.44	2.809 (5)	102.4
C12—H12A···Cg2ⁱ	0.96	2.85	3.545 (7)	130.4

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

References

Ali, R., Misra, B. & Nizamuddin, M. (1989). Indian J. Chem. Sect. B, 28, 526–528. Google Scholar
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Bruker (2003). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gunasekaran, B., Sureshbabu, R., Mohanakrishnan, A. K., Chakkaravarthi, G. & Manivannan, V. (2009). Acta Cryst. E65, o2069. Web of Science CSD CrossRef IUCr Journals Google Scholar
Seshadri, P. R., Balakrishnan, B., Ilangovan, K., Sureshbabu, R. & Mohanakrishnan, A. K. (2009). Acta Cryst. E65, o531. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany. Google Scholar
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2224

doi:10.1107/S1600536811030443

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access