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

Abstract

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,

• a = 6.6248 (4) Å

• b = 9.7172 (6) Å

• c = 21.2083 (11) Å

• V = 1365.27 (14) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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)

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811030443/bt5579globalsup2.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically and refined using riding model with C—H = 0.93Å and U_iso(H) = 1.2Ueq(C) for aromatic C—H, C—H = 0.96Å and U_iso(H) = 1.5Ueq(C) for methyl groups.

Figures

Fig. 1.

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

Crystal data

C12H11Br2NO2S	F(000) = 768
Mr = 393.10	Dx = 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

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

Refinement

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(Fo2) + (0.029P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3491 reflections	Δρmax = 0.47 e Å−3
165 parameters	Δρmin = −0.92 e Å−3
0 restraints	Absolute structure: Flack (1983), 1460 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.010 (10)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+1, y−1/2, −z+1/2.